Basic Chemical Bonding

Molecules are artwork just beautiful!

Cubane

Dodecahedrane

Side and top views of a single-wall Chemical Bonding Basic exohydrogenated carbon nanotube

Looking Back at Chemical Bonding

Bonding must be electric nature. 1852, E. Frankland proposed the valence concept, using for valence.

1857, F.A. Kekule figured out the structure of benzene C6H6.

1874 J.H. van't Hoff and le Bel postulated the tetrahedral arrangement of 4 bonds around carbon.

1916 G.N. Lewis propsed the dot symbol for valence electrons
1923 G.N. Lewis wrote Valence and the structure of atoms and molecules. 1939 L. Pauling wrote The nature of chemical bond 1940 N.V. Sidgwick and H.E. Powell studied the lone pairs of valence electrons.
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Lewis Theory
G.N. Lewis (1875-1946) recognized valence (outmost) electrons fundamental to bonding electron transfer resulting in ionic bonds sharing electrons resulting in covalent bonds atoms tend to acquire a noble-gas electronic configurations

The attraction between electrons of one atom to the nucleus of another atom contribute to what is known as chemical bonds.
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Lewis Dot Structure

Lewis wrote in a memorandum dated March 28, 1902

Basic Chemical Bonding

Lewis Dot Structure 2

Lewis' Paper of 1916 In this paper, Lewis begins by using cubes, but he moves away from them by the end of the paper. Here is how he visualized the elements lithium through fluorine:

Please illustrate modern Lewis dot structures of periods 2 and 3 elements. Chieh does that during lecture.
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Lewis Dot in Covalent Bond

Write the Lewis dot structures for these molecules:

HH, HCl, HOH, NH3, H, He, Cl, Ne H3O+, NH4+, OH , (coordinate covalent) Cl2, O2, (multiple bonds) N2, CO2
Explain the types in each line and write the dot structures.

Define: bond pair, lone pair, single bond, double bond, triple bond

Basic Chemical Bonding

Polar Covalent Bond & Electronegativity

Discuss the nature of these bonds: HF, HCl HOH (including lone pairs) Electronegativity: the ability of an element competing for bonding electrons.
The variation as a function of atomic number and its trends on the Periodic Table has been discussed previously, and the Periodic Table showing electronegativity is shown next.
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Periodic Table of Electronegativity

Basic Chemical Bonding

Covalent and Ionic Bonds

The ionicity of a bond depends on the difference in electronegativity. A difference of 1.7 is given as 50% ionic, and usually considered ionic. Analyze these

Basic Chemical Bonding

Electron Density of a Polar Bond LiH

Li H dipole moment
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Writing Lewis Dot Structures

Show all valence electrons. Each bond represents two electrons. All electrons are paired, usually (exceptions). Each atom acquires 8 valence electrons, usually (exceptions). Multiple bonds are needed sometimes. Show class how to write Lewis structure for CF4, (CX4, SiX4), NH3, H2O, HF C2H5OH, HCN, H3PO4, O=N=O
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Formal Charge
The formal charge on any atom in a Lewis structure is a number assigned to it according to the number of valence electrons of the atom and the number of electrons around it. The formal charge of an atom is equal to the number of valence electrons, Nv.e. subtract the number of unshared electrons, Nus.e. and subtract half of the bonding electrons, Nb.e..

Formal charge = Nv.e. - Nus.e. - Nb.e.

Stability rules: Formulas with the lowest magnitude of formal charges are more stable. More electonegative atoms should have negative formal charges. Adjacent atoms should have opposite formal charges.
Basic Chemical Bonding Explain & workout formal charge judge stability of a formula 12

Find Formal Charge

SO42 Find FC in these structures

Confirm these FCs

Basic Chemical Bonding

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Resonance
When several structures with different electron distributions among the bonds are possible, all structures contribute to the electronic structure of the molecule. These structures are called resonance structures. When two or more plausible Lewis structures can be written but the correct structure cannot be written is called resonance. For example:

..
O

..
O

..
O

:O:

:O :

:O:

:O:

:O:

:O :

Please complete the dot structure and find the formal charge for the above structures.
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Draw Resonance Structures

Draw resonance structures for these: CO2 NO2 NO2HCO2O3 SO3 NO3 :O::C::O: (plus two more dots for each of O) .NO (bent molecule due to the odd electron) 2 :NO2- (same number of valence electron as O3 & SO2) H-CO2 ( ditto) ozone consider O-SO2, and the resonance structures flat same number of valence electron as CO32-

Draw all resonance structures of all these

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Exceptions to the Octet Rule

Molecules with odd number of valence electrons, N=O (compare to CO), CH3, OH, H, NO2 etc. :Cl: :Cl: :Cl: / \ / \ / \ M M M M Molecules with incomplete octets, \ / \ / \ / BeCl2 AlCl3, (gas and polymeric for both), :Cl: :Cl: :Cl: BF , compare with NH BF , BF ,
3 3 3 4

M = Al or Be Expanded valence shells, PCl3, PCl5, SF6, H2SO4, H3PO4 Draw Lewis dot structures of all these molecules to see the exceptions
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Bond Properties
Bond length bond angle distance between the nuclei of bonded atoms angles for any two bonds around an atom

bond energy energy required to break the bond bond-dissociation energy

Bond Length Energy 348 614 839 Compound H2 HF H2O NH3 CH4 length energy Bond (pm) (kJ/mol) HH FH OH NH CH 74 92 96 101 109 436 565 464 389 414
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C C 154 C = C 134 C C 120

O O 148 O = O 121

145 498

Discuss the variations of bondBasic Chemical Bonding energy length and bond

VSEPR Theory
Valence-Shell Electron Repulsion Theory: The VSEPR model counts both bonding and nonbonding (lone) electron pairs (E), and call the total number of pairs number of electron groups (Neg). If the element A has m atoms bonded to it and n nonbonding pairs (E), then Neg = m + n Discuss the electronic and molecular structures of CH4, ENH3, & E2OH2. All have Neg = 4. Bond angles in these structure indicates that E E repulsion is stronger than that of bonding electrons.

CH4

ENH3
Basic Chemical Bonding

H2OE2

HFE3
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Shape of Molecules
During the lecture, we will discuss structures of the following: Make sure you can draw and name the AX2 linear geometrical shape of these structures. BeCl
2

AX3, AX2E triangular planar, bent BF3, SO2E AX4, AX3E AX2E2 tetrahedral, pyramidal, bent AX5, AX4E, AX3E2, AX2E3 triangular pyramidal, butterfly PCl5, SF4E, ClF3E2, XeF2E3 T-shape, linear AX6, AX5E, AX4E2 octahedral, square pyramidal, square planar SF6, BrF5E, XeF4E2, ICl4E2 AX4E, whats my shape?
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Chemistry and Molecular Shapes

Neg Example 2 3 4 Descriptor BeCl2, CO2 Linear BF3, SO3 Trigonal planar SO2E, OO2E Bent CH4 NH3E H2OE2 PF5 SF4E ClF3E2 Tetrahedral pyramidal Bent Trigonal bypyramidal Seesaw, butterfly T-shape

Neg Example 6 SF6, OIF5 BrF5E XeF4E2

Descriptor Octahedral Pyramidal Square planar

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Basic Chemical Bonding

Structures with Multiple Covalent Bonds

We will talk about pi (p) bonding later. At this stage, you may consider all electrons in a multiple bond are confined around the lines connecting the two atoms. Thus the number of electron groups Neg for a multiple bond is 1. For example, Neg = 3 for

..
S / ::O: \\

\
C=O / H

:O:

What is the Neg for SO42, COS, N2O?

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Molecules with more than one central atom

Describe the structure of methyl isocyanate, CH3NCO. Draw the skeleton and add all valence electrons

H3C N C O
Draw the Lewis dot structure that satisfy the octet rule. N=C=O
120o 180o

H-C H

109o

What are the formal charges of all atoms in both structures? Describe the structures of C2H5OH, CH3CO2H, and H2NCH2CH2(OH)COOH. Basic Chemical Bonding

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Dipole Moment
The product of magnitude of charge on a molecule and the distance between two charges of equal magnitude with opposite sign is equal to dipole moment; D (unit is debye, 1 D = 3.34E30 C m (coulumb.metre); representation Cl+H, a vector ) Dipole moment = charge x distance Symbol: = e x d = dq * dbond
For Cl+H, = 1.03 D, dHCl = 127.4 pm Two ways of lookint at H+Cl, dq = 1.03*3.34e30 C m / 1.274e-12 m = 2.70e-20 C (charge separation by HCl )

Ionic character = dq / e = 0.17 = 17% d = 3.44e-30 C m / 1.60e 19 C (e charge)

Basic 0.215 Bonding = 2.15E11 m = 0.215 pm (+e byChemicalpm)

mHCl = 1.03 D mHF = 1.9 D, find d and % ionic character for them.
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Dipole moment of H2O

Verify please: The dipole moment of individual water molecules measured by Shostak, Ebenstein, and Muenter (1991) is 6.1871030 C m (or 1.855 D). This quantity is a vector resultant of two dipole moments of due to OH bonds. The bond angle HOH of water is 104.5o. Thus, the dipole moment of a OH bond is 5.0531030 C m. The bond length between H and O is 0.10 nm, and the partial charge at the O and the H is therefore q = 5.0531020 C, 32 % of the charge of an electron (1.60221019 C). Of course, the dipole moment may also be considered as separation of the electron and positive charge by a distance 0.031 nm. For the water molecule, a dipole moment of 6.1871030 C m many be considered as separation of charge of electron by 0.039 nm.
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Dipole moment and Molecular Shape

Dipole moments are vectors. The net dipole moment of a molecule is the resultant (vector sum) of all bond-dipole-moment.

Answer & explain these: mHH = ____ mO=C=O = _____ mCH4 = _____ mCCl4 = _____ mBF3 = _____ mH2O = 1.84 D mO3 = 0.534 D (implication of long pair) Which are polar and non-polar, SF6, H2O2, C2H4, Cl3CCH3, PCl5, I-Cl, NO, SO2, CH2Cl2, NH3, (put your skill to tell molecular shape at work)
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Review 1
Predict the molecular geometry of the polyatomic anion ICl4 Hint: Draw the Lewis dot structure for Cl and I (figure out the valence es) Drew the Lewis dot structure for ICl4

What is the number of unshared e of the above?

Drew the ion, and describe this shape in proper term.

Do the same for NCl3, POCl3, COS, H2CO,

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Review 2
Apply bond energy for thermochemistry calculation In a chemical reaction, add (ve) energy released from bonds formed and (+ve) energy required to break the bonds is the energy of the reaction DHrxno. Data:

What is the heat of reaction for 2 H2 (g) + O2 (g) 2 H2O (g), DHrxno = 2 * D (HH) + D(O=O) 4 * D(HO)

D(O=O) = 498 kJ mol1 D(HH) = 436; D(HO) = 464;

2 H (g) H2 (g), DH = D (HH) H2 (g) H (g), = 2 * 436 + 489 4*464 DH = D (HH) = 495 kJ compare to DHfo = 248 kJ mol1 of H2O

Basic Chemical Work on example 11-14 on page 423 Bonding

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Review 3
What is the energy of reaction for CH4 (g) + Cl2 (g) CH3Cl (g) + HCl (g)?

Data: D(C-H) = 414 kJ mol1 D(ClCl) = 243 D(C-Cl) = 339 D(HCl) = 431

Solution:

H3C H + Cl Cl H3C Cl + H Cl + 414 + 243 339 431 kJ DHrxno = + 414 + 243 339 431 kJ = 113 kJ

Answer: 113 kJ is released in this reaction.

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