CHAPTER 1

BONDING IN ORGANIC COMPOUND
BY: Dr Nurziana

• An atom is the smallest particle that comprises a chemical element.

Elements And Compounds

• It consists of an electron cloud that surrounds a dense nucleus. The cloud is made up of negatively charged electrons. • This nucleus contains positively charged protons and electrically neutral neutrons, • When the number of protons in the nucleus equals the number of electrons, the atom is electrically neutral. • An atom is classified according to its number of protons and neutrons: the number of protons determines the chemical element and the number of neutrons determines the isotope of that element. • A molecule is defined as group of at least two atoms in a definite arrangement held together by very strong chemical bonds .

Electron Configuration
• • • Atomic number: the number of protons (or electrons) in the nucleus. In other words, each element has a unique number that identifies how many protons are in one atom of that element. Mass number: the number protons and neutrons in its atoms. Atomic mass: A total mass of protons, neutrons and electrons in a single atom. Weighted average of an element. Example: Isotopes of 81Br (35p + 46n) and 79Br (35p+44n). So the atomic weight is 79.9 Isotopes: Atoms of the same element can have different numbers of neutrons; the different possible versions of each element. So they have same atomic number but different mass number. Example:

b) Atomic Orbitals

• Electrons are described as residing in particular shells or energy level. • Each shell has a certain capacity for electrons. Electrons occupy specific atomic orbitals. • Atomic orbital – the space in which an electron may be found around a single atom in a particular state energy. • The shape and geometric orientation of space occupied by electrons are described by s, p, d and f orbitals.

• An s orbital is spherical.

• The first electron shell is 1s and contain just 1s orbital. • Second electron shell has two different kinds of orbitals which are 2s and 2p. • A p orbital has 2 lobes with the atom’s nucleus located between the 2 lobes.

•Each shell except the first has 3 p orbitals (Px, Py and Pz) identical in energy, size, shape and perpendicular to one another.

c) Filling Atomic Orbitals AFBAU PRINCIPLE
-

The atoms which have more than 1 electron, electrons are placed in the lowest energetically available subshell. 

HUND’S RULE -If two or more energetically equivalent orbitals are available

(e.g., p, d etc.) then electrons should be spread out before they are paired up (Hund's rule).

d) Electron Configuration and Periodic Table

 Period 1: 1H and 2He – represent orderly completion of first energy level and 1s orbital.  Period 2: 3Li and 4Be complete the 2s orbital. : 6 elements (B, C, N, O, F and Ne) the three p orbitals are occupied.  Period 3: the 3s (2 electrons, 2 elements) and 3p (6 electrons 6 elements) are being filled. : It begins with 11Na (1s2 2s2 2p6 3s1) and ends with 2 2 6 2 6 18Ar (1s 2s 2p 3s 3p ).  As a result, group I and II filling s orbitals, groups III to VIII filling p orbitals.  Elements within a particular group show similar chemical properties.

• • • • •

The octet rule states that atoms tend to combine in such a way that each have eight electrons in their valence shells, giving them the same electronic configuration as a noble gas (s2p6) Noble gases - eight electrons in the valence (outer most) shell (with the exception of He which has two electrons). The rule is applicable to the main-group elements, especially carbon, nitrogen, oxygen, and the halogens, Atoms can form stable electron configurations like noble gases by losing electrons, gaining electrons and sharing electrons. Atoms that have 1, 2 or 3 electrons in their outer shells will tend to lose them in interactions with atoms that have 5, 6 or 7 electrons in their outer shells. Atoms that have 5, 6 or 7 electrons in their outer shells will tend to gain electrons from atoms with 1, 2 or 3 electrons in their outer shells. Atoms that have 4 electrons in the outer most energy level will tend neither to totally lose nor totally gain electrons during interactions and thus they tend to share electrons.

Stable Octets

Ionic (Electrovalent) Bonding
• An ionic bond (or electrovalent bond) is a type of chemical bond that form between metal and non-metal ions. In short, it is a bond formed by the attraction between two oppositely charged ions. In ionic bonding, metal atoms lose electrons and non-metal atoms  gain electrons to form ions, which are then held together by strong electrostatic interactions.  An ionic bond involves the transfer of electrons.  The metal donates one or more electrons, forming a positively charged ion or cation with a stable electron configuration. These electrons then enter the non metal, causing it to form a negatively charged ion or anion which also has a stable electron configuration. Ionic bonding will occur only if the overall energy change for the reaction is favourable, the low electronegativity of metals and high electronegativity of non-metals means that the energy change of the reaction is most favorable when metals lose electrons and nonmetals gain electrons.

• The larger the difference in electronegativity between two atoms, the more ionic the bond. • Electronegativity – Is a measure of the tendency of an atom to attract a bonding pair of electrons

2.8.1

2.8

2.8.7

2.8.8

[

 

]+ [

]-

Covalent Bonding
• Covalent bonding- involve the sharing of electron pairs between atoms. • Each atom donates half of the electrons to be shared • covalent bonding does not necessarily require the two atoms be of the same elements, only that they be of comparable electronegativity. • To depict covalent bonds in molecules : Lewis dot Structure and line bond formula

To draw an electrons dot formula (Lewis dot structures) of the organic compound (example: CH4) 1) determine the number of electrons available for the formula 2) Hydrogen is in column IA and thus has 1 electron. Since there are 4 hydrogen atoms, the total for hydrogen will be 4 electrons. Carbon is in column IVA and thus has 4 outer electrons... 3) determine which atom will be in the center of the molecule. Hydrogen atoms are only able to form one bond to other atoms so we need to put the carbon atom in the center. 4) draw all of the other hydrogen atoms around the carbon atom and place 2 electrons between these hydrogen atoms and the carbon atom. This gives you a total of 8 electrons.

Electron structures involving multiple bonds

Multiple equivalent structures: resonance

• Polyatomic Ions and Formal Charge -polyatomic ion – is a charged species
nitrate NO3 -1 hydroxide OH
-1

composed of two or more atoms covalently bonded.
chromate CrO4 -2 cyanide CN
-1

chlorate ClO3 -1 dichromate Cr2O7 -2 ammonium NH4 +1    

sulfate SO4 -2 phosphate PO4 -3 carbonate CO3 -2 acetate C2H3O2 -1

The formal charge on an atom is the electric charge it would have if all bonding electrons were shared equally with its bonded neighbors. -is a accounting procedure to determine the location of charge in a molecule as well as compare how good Lewis structure might be.

Formal charge-

FC = GN - UE -1/2BE FC = Formal charge GN =Periodic table group number (number of valence electrons in free) UE = number of unshared electrons BE = number of electrons shared in covalent bonds.
To calculate the formal charge on nitrogen there are three pieces of information that you need to know: • the group number (number of valence electrons), the number of non-bonding electrons, and the number of shared electrons. Nitrogen is in group five; thus, it has five valence electrons • Number of non-bonding electrons: there are no non-bonding electrons, so this is zero • Number of shared electrons: there are four bonds, and there are two electrons in each bond, so this number is eight formal charge = 5 - 0 - 0.5(8) = +1 Thus, the nitrogen has a formal charge of +1

• Polar bonds: Is a covalent bond in which there is a separation of charge between 2 atoms – one atom is slightly positive and the other is slightly negative. Example: HCl

• How are electrons shared to form covalent bonds? Overlapping the atomic orbitals. • Sigma, σ bond is formed head to head overlap of atomic orbital in one position • Pi, π bond is formed when parallel p orbitals each with one electron overlap in two positions.

An Orbital Approach to Covalent Bonding

Sigma, σ bond

Pi, π bond

• Electron configuration for carbon: carbon has 4 electrons in its outer shell 2s2 2px1 2py1 • Carbon tetravalence is explained by exciting one 2s electron to a 2p orbital – creating 4 unpaired electrons during bonding.

• Shapes of organic molecules – atoms are oriented in a molecule so that the repulsion between the electron pair (bonding or nonbonding) around an atom is minimized. • Carbon will have 4, 3 and 2 atoms bonded to it.

Carbon bonded to 4 atoms
• Example: methane, CH4. • To satisfy the valence of all 5 atoms, each of H must be bonded to the carbon by a single bond. • The hydrogen must be put at maximum distances from one another to reach most stable molecular geometry. • 1s orbital (H atom) and 2s 2px 2py 2pz (C atom is in excited state) are hybridized (blend) to form 4 new orbitals that are equivalent and at the ideal 109.5o angle from one another • The new sp3 hybrid orbitals are formed, composed from 1s and three p orbitals. • The geometry formed is tetrahedron. • 4 sigma bonds were formed.

Carbon bonded to 3 atoms
• Example: Ethylene, CH2=CH2 • Central atom, C is bonded to three atoms and the possible arrangement that allows three atoms bonded to a central carbon is trigonal with the angle of 120o. • The outer shell must be hybridized to create an orbital geometry consistent with the preferred trigonal shape. • Only 3 orbitals have to be hybridized, where s and two p orbitals are combined to form a new sp2 hybrid orbitals. • These sp2 orbitals are directed towards the corner of an equilateral triangle. • An unhybridized p orbital remains unchanged on each carbon, perpendicular to the hybridized orbitals whose axes all lie in one plane.

• Overlap of two sp2 hybrid orbitals of carbons forming a sp2 -sp2 σ bond • The unhybridized p orbitals of carbons are parallel to each other, both lobes of that p orbitals merge above and below σ bond forming p-p π bond. As a result, carbon-carbon double bond is composed from a σ bond and a π bond. • The s-sp2 σ bonds are also formed by overlapping each remaining sp2 hybrid orbitals of the carbons with a spherical s orbital of a hydrogen.

Carbon bonded to 2 atoms
• Example : acetylene CHΞCH • The bonded atoms are on opposite sides of the central carbon at a maximum distances in a linear geometry of 180o bond angles. • A carbon 2s orbital hybridizes with only a single p orbital resulting sp hybrid orbitals and two p orbitals remain unchanged. • When sp hybridized carbon atoms approach each other, the hybrid orbital overlap head on to form strong sp-sp σ bond, the 2 unhybridized p orbitals of carbons form 2 p-p π bonds resulting formation of carbon-carbon triple bonds. • A spherical s orbital of hydrogen hybridizes with the remaining 2p orbital of carbon to form s-sp σ bond to complete the acetylene molecule.

HYBRIDIZATION OF OTHER ATOM: NITROGEN AND OXYGEN
Oxygen has 2 pairs nonbonding electrons.

 O has 2 single bonds & 2 pairs of nonbonding electrons – four space occupying group – O is sp3 hybridized 2 orbitals have one electron each and overlap with orbitals from C and H to form a σ bonds.

O has double bond and 2 pairs nonbonding electrons. The O is sp2 hybridized, two of three sp2 orbitals occupied by nonbonding electrons pairs The remaining sp2 orbital and unhybridized orbital overlap each other to form σ and π double bond.

Nitrogen has one pair nonbonding electrons. So the atom can have 3 (sp3), 2 (sp2)or 1 (sp) bonded atoms.

Sign up to vote on this title
UsefulNot useful