PHYSICAL PROPERTIES RELATIONSHIPS

The structures of organic molecules vary widely. Within this variety there are similarities in structure that result in similarities in chemical, physical, and/or biological properties. If one can understand the properties of a compound based on its structure, then we might be able to predict properties of a compound with similar structure. The power to predict the properties of a substance based on its similarity to other substances of known structure is a powerful tool for organic chemists, especially so for the discovery of new pharmaceuticals. It is useful, therefore, for you to learn to recognize various categories of structural relationships.

Structure Basic 1 of Organic Molecules

STRUCTURE BASIC 1
Shape of Molecules: Atomic Orbitals, Covalent bond, sigma bond and pi bond, Hybridization of carbon orbital : Sp3 (single bond, tetrahedral), Sp2 (double bond, planar),sp (triple, linier), Non covalent Interaction : dipole interaction, London dispersion, hydrogen bond, Physical properties : Polarity, Solubility, Boiling & Melting point,,

: Atomic Orbitals, Covalent bond, sigma bond and pi bond, Shape of Molecules : Hybridization of carbon orbital : Sp3 (single bond, tetrahedral), Sp2 (double bond, planar),sp (triple, linier), 3-D drawing, Rotation around single bond : Conformer , Newman Projection, Isomer ,

Rigid structure of double bond : Stereoisomer (Cis/trans and E/Z structure designation ), CahnIngold-Prelog Rules, Enantiomer and R/S structure designation),
4

 Objectives Know how atomic orbitals overlap to form molecular orbitals Understand orbital hybridization Using the VSEPR model, predict the geometry of molecules Understand the formation of molecular orbitals

ATOM AND ITS ELECTRONS

The basic unit of matter is an atom. It consists dense central nucleus surrounded by negatively charged electrons. The nucleus contains a mix of positively charge proton and electrically neutral neutrons. The electrons of an atom are bounded to the nucleus by electromagnetic force

The electrons determine the chemical properties of an element .

ATOMIC ORBITALS
, the orbiting electron around a nucleus could not fully describe as particles, in the sense of a planet orbiting the sun. It is treated by the wave-particle duality, so that the orbital exist as standing waves.
In quantum mechanics

The atomic orbitals are supposed to describe the shape of the atmosphere(electron) distributed around a relative tiny planet (nucleus)

ATOMIC ORBITALS
, an atomic orbital is a MATHEMATICAL FUNCTION that describes the wave-like behavior the electrons in an atom
In quantum mechanics

The function can be used to calculate the probability of finding any electron of an atom in any specific region around atoms nucleus.

The simple names s orbital, p orbital, d orbital and f orbital refer to subshell s, p, d and f respectively.

Graphical representation of the 1s atomic orbital of H

10

ORBITALS are interact each other like Waves

Waves that are in phase : add together, increase amplitude. Waves that are out of phase : cancel out

on the same atom is HYBRIDIZATION between different atoms is BOND FORMATION

11

SIGMA BONDING

sigma bonds ( bonds) are formed by head-on overlapping between atomic orbitals
A bond may be formed by s-s, p-p, s-p, or hybridized orbital overlaps. a -bond is symmetrical with respect to rotation about the bond axis
12

Shape of Methane
109o

TETRAHEDRAL

 The molecular geometry depends on the electron pair geometry (i.e. the total number of electron pairs on the central atom).

the shapes of the molecule is explained by Valence Shell Electron Pair Repulsion (VSEPR) model, that states that electron pairs arrange themselves a maximum distance apart.

GEOMETRY OF METHANE
base on VSEPR MODEL .

in methane, the central carbon atom is bonded to four other identical atoms The electron pairs ( electron bond) strive to be as far apart from other electron pairs as possible. This arrangement places the four identical atoms, the hydrogens, toward the corners of a regular tetrahedron with the atom they are bonded to.

15

FOR CARBON WITH 6 ELECTRON What its electron configuration?

16

order for filling the orbitals:

17

Hund's Rule applied to the filling of the atomic orbitals of carbon

Based on this electron configuration, Carbon has 4 outershell electron 2 in s orbital and 2 in p orbital Which in different level of energy

So If C bonded with 4 H, the bonds would have been non identical

Since actually they are identical, must the for orbital (s 2 and 2 p) are fused or combine to form a new orbital or hybrid orbital This fenomena is called hibrization
18

SP3 hybridization of C

Electron configuration of carbon (a) before and (b) after hybridization. Note that the energy level of the hybrid orbitals is between that of the 2s and that of the 2p orbitals.
19

Mixing, or hybridization, of one s orbital with three p orbitals produces four sp3 orbitals. Each of the sp3 orbitals has 25% s character and 75% p character.
20

Bonding in CH4

22

PLANAR SHAPE OF C2H4

H 120 H C C

H sp 2 H

SP2 hybridization CARBON ATOM

in Ethylene (CH2=CH2)

Both carbons in ethylene are sp2 hybridized and bonded to each other
24

Pi BONDING
Sideways overlap of parallel p orbitals.

25

Orbital Overlap in Ethylene

A double bond consists of A SIGMA BOND and A PI BOND.

26

ORBITAL OVERLAP INI ACETYLENE

linier

27

SP hybridization

28

SP hybridization

The molecular orbitals in acetylene are formed from overlap of the p orbitals of two sp hybridized carbon atoms.
29

LINIER SHAPE OF MOLECULE P INI ACETYLENE

=>

30

Orbital Hybridization
BONDS 2 3 4 SHAPE linear trigonal planar HYBRID REMAIN sp sp2 2 ps 1p none

tetrahedral sp3

MOLECULAR SHAPES of oxygen/nitrogen containing compound

Case 1Amonia
:NH3

3 Sigma bonds and one lone pair

N
H
Geometry? pyramidal

H H
WHY?

See nucle, not electrons

33

Case 2
Water and CH3OCH3

2 sigma bonds and 2 lone pair

BENT
H H
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Central Atoms with Single-Bond Pairs and Lone Pairs

Lone pairs of electrons are more repulsive than bonding pair electrons.

Central Atoms Multiple Bonds

To predict geometry, count the multiple bond as a single bonding pair of electrons.

Case 3 Etanal
One s orbital + Two pi orbitals

3 sp2 orbitals

trigonal planar: 120o bond angles.

Carbon has 3 sigma and one pi bond

H3C

H
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Central Atoms Surrounded by Only Single-Bond Pairs

Central Atoms with Single-Bond Pairs and Lone Pairs

Case 4 HYDROGENCIANIDE Carbon has sp Hybrid Orbitals Linear 180 o

Combine one s 2 with one p 2 sigma orbital

H-C
H-C N

Note: both C and N are sp hybridized

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identification of bonding and geometry in Glycine

sp
3

H N sp
3

O C

sp

C H H

O H sp
3

Bonding in Glycine
sp
3

H N sp
3

O C

sp

C H H

O H sp
3

Bonding in Glycine
sp
3

H N sp
3

O C

sp

C H H

O H sp
3

Bonding in Glycine
sp
3

H N sp
3

O C

sp

C H H

O H sp
3

Bonding in Glycine
sp
3

H N sp
3

O C

sp

C H H

O H sp
3

QUIZES
Predict the hybridization, geometry, and bond angle for each atom in the following molecules: NH2NH2 Caution! You must start CH3-CC-CHO with a good Lewis
O CH3 C _ CH2
structure

47

POLARITY

Tendency of a molecule, or compound, to be attracted or repelled by electrical charges because of an asymmetrical arrangement of atoms around the nucleus.

48

BOND POLARITY
When two dissimilar atoms bond, the electrons are shared unequally and result in a partial negative charge (d-) on one atom and a partial positive charge (d+) on the other atom.
POLAR COVALENT BOND

Bond polarity depends on the electronegativity of the atoms.

ELECTRONEGATIVITY
Electronegativity (c) of an atom is the atoms ability to attract electrons to itself. c increases c decreases

Measure of POLARITY
Bond Dipole Moments (debyes)

d+

d-

C
2,5

O
3,5

= 4.8 x d (electron charge) x d(angstroms

Product of the magnitude of the partial charges and the distance by which they are separated

51

POLAR MOLECULES orientation under electrical field

blue indicates high electron density and red indicates low

HCl highly polar. Between two electric plates with the field off, the molecules lie every which way (oriented randomly) With the field on, however, they become oriented with their negative ends facing the positive plate and their positive ends facing the negative plate.

RELATIVE STRENGTH OF MOLECULAR POLARITY

=>

The bigger the partial charges, the more the polarity of the bon
53

INFLUENCE MOLECULAR GEOMETRY ON POLARITY

=>
Vector sum of the bond dipole moments. Lone pairs of electrons contribute to the dipole moment.
54

Molecular Polarity A molecules polarity is a function of the molecular shape and the electronegativity of the atoms.

PHYSICAL PROPERTIES OF HYDROCARBONS

56

PHASES OF MATTER
Matter can exist in four phases (or states), solid, liquid, gas, and plasma,
A solid is matter in which the molecules are very close together and cannot move around

In a liquid, the molecules are close together and move around slowly In A gas the molecules are widely
separated, move around freely, and move at high speeds. A plasma is a gas that is composed of free-floating ions (atoms 57 stripped of some electrons - positively charged) and free electrons

In a liquid the molecules are packed closely together with many random movements possible as molecules slip past each other. As the temperature increases, the kinetic energy increases which causes increasing molecular motion (vibrations, slipping pass each other). Eventually, motion becomes so intense that the forces of attraction between the molecules is disrupted to the extent the molecules break free of the liquid, become a gas.

Water Liquid to Water Gas: This animation shows how water molecules are able to break the forces of attraction i.e. the hydrogen bonds to each other and escape as the gas molecule. This is what is happening inside the gas bubble as it is rising to the surface to break and release the water gas molecules.

BOILING POINT
The temperature at which the vapor pressure of the liquid equals the environmental pressure surrounding the liquid. At that T, the P of the liquid becomes sufficient to
vapor

overcome Patm and allow bubbles of vapor to form inside the bulk of the liquid.

MELTING POINT
Pure, crystalline solids have a characteristic melting point, the temperature at which the solid melts to become a liquid. The transition between the solid and the liquid is so sharp for small samples of a pure substance that melting points can be measured to 0.1oC. The melting point of solid oxygen, for example, 60 is
o

Molecules which strongly interact or bond with each other through a variety of intermolecular forces can not move easily or rapidly and therefore, do not achieve the kinetic energy necessary to escape the liquid state. Therefore, molecules with strong intermolecular forces will have higher boiling points. This is a consequence of the increased kinetic energy needed to break the intermolecular bonds so that individual molecules may escape the liquid as gases.

Principle:
The greater the forces of attraction the higher the boiling point or the greater the polarity the higher the boiling point.

HYDROCARBON BOILING POINT

the longer the straight chain, the higher the boiling point -- van der Waals forces
isomers that are branched have lower boiling points hydrogen bonding increases boiling points

WWU Chemistry

the boiling points of straight chain alkanes are related to the number of carbon atoms in their molecules. Increased intermolecular attractions are related to the greater molecule-molecule contact possible for larger alkanes. Branched alkanes have less surface area contact, so weaker intermolecular forces.

BOILING POINTS OF ALKANES

The boiling point vary directly with the number of carbon atom
vary inversely directly proportional inversely proportional

64

As a rule of thumb, the boiling point rises 2030 C for each carbon added to the chain
Alkane
Methane Ethane Propane Butane Pentane Hexane Heptane Octane Nonane Decane Undecane Dodecane Icosane Triacontane Tetracontane Pentacontane

Formula
CH4 C2H6 C3H8 C4H10 C5H12 C6H14 C7H16 C8H18 C9H20 C10H22 C11H24 C12H26 C20H42 C30H62 C40H82 C50H102

Density Boiling point Melting point [gcm3] (at [C] [C] 20 C) -162 -183 gas -89 -172 gas -42 -188 gas 0 -138 gas 36 -130 0.626(liquid) 69 -95 0.659(liquid) 98 -91 0.684(liquid) 126 -57 0.703(liquid) 151 -54 0.718(liquid) 174 -30 0.730(liquid) 196 -26 0.740(liquid) 216 -10 0.749(liquid) 343 37 solid 450 66 solid 525 82 solid 575 91 solid

65

MELTING POINTS OF ALKANES

=>

Branched alkanes pack more efficiently into a crystalline structure, so have higher m.p.
66

What is the state (solid, liquid, gas) of alkane compound at 20C

67

68

2-methylpropane and n-butane which boil at higher temperatur and why

(2-methylpropane) and n-butane (butane), which boil at 12 and 0 C

2,2-dimethylbutane and 2,3-dimethylbutane which boil at higher temperature?

2,2-dimethylbutane and 2,3-dimethylbutane which boil at 50 and 58 C,

two molecules 2,3-dimethylbutane can "lock" into each other better than the cross-shaped 2,2-dimethylbutane, hence the greater van der Waals forces.

due to the greater surface area in contact, thus the greater van der Waals forces

69

Match each boiling point to the appropriate C7H16 isomer: 98.4 C, 92.0 C, 79.2 C.

70

m.p., b.p., and solubility; esp. for solids and liquids are influenced by the strength of attractions between molecules or INTERMOLECULAR INTERACTION

71

INTERMOLECULAR FORCES

Classification depends on structure.

Dipole-dipole interactions London dispersions Hydrogen bonding =>

72

DIPOLE-DIPOLE FORCES (permanent dipole) Between polar molecules Positive end of one molecule aligns with negative end of another molecule. Lower energy than repulsions, so net force is attractive.

73

Dipole-Dipole INTERACTION

=> Larger dipoles cause higher boiling points and higher heats of 74 vaporization.

LONDON DISPERSION FORCE instantaneously induced dipoles

Between nonpolar molecules Temporary dipole-dipole interactions Larger atoms are more polarizable..

75

Dispersions

=>
76

London Dispersions
Branching lowers b.p. because of decreased surface contact between molecules.
CH3
CH3 CH2 CH2 CH2 CH3 n-pentane, b.p. = 36C

CH3 H3C C CH3 CH3 neopentane, b.p. = 10C

CH3 CH CH2 CH3 isopentane, b.p. = 28C

=>
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Branched Alkanes
CH3
CH3 CH3
CH CH2 CH2 CH3 bp 60C mp -154C
CH3
CH3 CH CH

CH3
CH3

CH3 C CH2 CH3 CH3

bp 58C mp -135C

bp 50C mp -98C

=> Lower b.p. with increased branching Higher m.p. with increased branching

78

Intermolecular forces also help explain other liquid properties such as viscosity and freezing points. Based on their intermolecular attractions, try to rank pentane, octane, and decane in order of increasing viscosity. Assign "1" to the least viscous ("thinnest") of the three. What can you infer about intermolecular attractions in decane compare to those in pentane?

79

CH3CH2OCH2CH3 and CH3CH2CH2CH2OH

Are they isomer? What isomer type? Which one has higher boiling point /density

BP = 34.5C d = 0.7138 g/mL insoluble in water

BP = 117.2C d = 0.8098 g/mL soluble in water

80

Hydrogen Bonding
Strong dipole-dipole attraction Organic molecule must have N-H or O-H. The hydrogen from one molecule is strongly attracted to a lone pair of electrons on the other molecule. O-H more polar than N-H, so stronger hydrogen bonding =>
81

H Bonds

=>
82

If water behaved as a normal polar molecule it would have boiled at about - 100 C (shown in red). Instead, water boils at +100 C, which isthe very The major reason is strong abnormal. attractions afforded by the
hydrogen bonds. It takes a lot more kinetic energy in increasing T to break the H-bonds to free the water molecules as the gas.

More normal behavior is seen in dimethyl ether (CH3)2O which has no hydrogen bonds possible.

hidrogen bonding increase the Boiling Points

CH3
H3C N CH3 CH3

CH2

OH
CH3CH2

CH3

O CH3

ethanol, b.p. = 78C

dimethyl ether, b.p. = -25C

N CH3 H CH3CH2CH2 N H H propylamine, b.p. 49C

trimethylamine, b.p. 3.5C

ethylmethylamine, b.p. 37C

CH3

CH2

OH

CH3

CH2

NH2

ethanol, b.p. = 78C

ethyl amine, b.p. 17C

=>

polar dipole forces exerts a very strong effect to keep the molecules in a liquid state until a fairly high temperature is reached.

84

SOLUBLE AND INSOLUBLE

Soluble and insoluble. Alcohol is soluble in water; when added to water, it forms a clear solution. Oil is insoluble in water; when added to water, the two liquids form separate layers.

85

SOLUBILITY
Like dissolves like Polar solutes dissolve in polar solvents. Nonpolar solutes dissolve in nonpolar solvents. Molecules with similar intermolecular forces will mix freely. =>
86

SOLUBILITY is an ability of a substance to dissolve. In the process of dissolving, the substance which is being dissolved is called a solute and the substance in which the solute is dissolved is called a solvent. A mixture of solute and solvent is called a solution.

SOLUBILITY is understood as a maximum amount of solute that dissolves in a solvent at so called equilibrium. An equilibrium is a state where reactants and products reach a balance - no more solute can be dissolved in the solvent in the set conditions (T,P). Such a solution is called a saturated solution. 87

CH3CH2OCH2CH3 and CH3CH2CH2CH2OH Are they isomer? What isomer type? Which one dissolves in water? Both?

BP = 34.5C

BP = 117.2C

d = 0.7138 g/mL

d = 0.8098 g/mL

insoluble in water

soluble in water

88

PROCESS OF DISSOLVING

Why some things dissolve and some do not?

When dissolving, new bonds (Intermolecular forces) between solvent and solute are created. During this process energy is given off. The amount of this energy is sufficient to brake bonds between molecules of solvent and between molecules of solute.
If the energy resulted from the intermolecular forces is not enough to disrupt molecular bond of solvent and molecular bond of solute, then the solute will not dissolve.
89

Ionic Solute withPolar Solvent

Energy released is enough

=>
90

Ionic Solute with Nonpolar Solvent

Energy released is not enough

=>
91

Nonpolar Solute with Nonpolar Solvent

Energy released is enough

=>
92

Nonpolar Solute with Polar Solvent

Energy released is not enough

=>
93

II. Structure and Physical Properties: RX

Bonding in alkyl halides:
Bond lengths increase as size of halogen increases: C-I > C-Br > C-Cl > C-F polar covalent bonds sp3 hybridized tetrahedral

II. Structure and Physical Properties: RX

Polarity:
dipole-dipole interactions dipole-induced dipole interactios

Boiling points are highest for iodine containing compounds, lowest for fluorine compounds of similar molecular weight: R-I > R-Br> R-Cl > R-F
Polarizability: ease with which electron distribution is affected by nearby electric field accounts for induced dipole interactions

Insoluble in water Higher density than water

II. Structure and Physical Properties: R-OH

Polar sp3 hybridized bent hydrogen-bonding relatively high boiling points
R O H R R O H H O H O R

Boiling Points:
Alcohols have high boiling points Boiling Point Intermol.
Attractions CH3CH2CH3 - 42o C CH3OCH3 CH3CH2OH - 24o C 78o C London Dipoledipole Hydrogen bonding

Solubility:
alcohols having from 1 to 4 carbons: miscible with water alcohols having from 4 to 6 carbons: slightly soluble alcohols having greater than 6 carbons are insoluble
polyols (diols, triols, etc.) are very soluble