Chapter 1 General Chem Review '13 BW

Organic Chemistry!
! Denition of Organic Chemistry: !
Chapter 1. A Review of General Chemistry! ! "

Junha Jeon !
Department of Chemistry ! University of Texas at Arlington ! Arlington, Texas 76019 ! " ! Chem 2321, Fall 12 ! !
The study of carbon-containing molecules (structures) and their reactions! ! ! During a reaction?! A collision! bonds are breaking and forming; the motion of electrons" ! FOCUS on the electrons.! !
Structure and Reaction of Organic Molecules!

! Denition of Organic Chemistry: ! The study of carbon-containing molecules (structures) and their reactions! ! ! Structure:! A specic arrangement of atoms! ! ! Reaction:! A chemical process in which two or more substances act mutually on each other and are changed into different substances, or one substance changes into two or more other substances." ! !
Electron Movements!
! Denition of Organic Chemistry: ! The study of carbon-containing molecules (structures) and their reactions! ! ! During a reaction?! A collision! bond(s) is(are) breaking and forming; the motion of electrons" ! ! FOCUS on the electrons.! !
Electron Movements!
Electron Movements!
1 !
Structural Theory: Constitutional Isomer!
Lets focus on structure and properties of organic molecules!
Constitutional isomer: the same molecular formula (CH4N2O), yet the constitution (connectivity) of the atoms are different. ! " Different physical property (e.g. boiling point)!
Structural Theory: Constitutional Isomer!
Structural Theory!
Valence: the number of bonds usually formed by each element! Predict a structure of organic compounds! ! Atoms that are most commonly bonded to carbon include N, O, H, and halides! (F, Cl, Br, I)! ! With some exceptions, each element generally forms a specic number of ! bonds with other atoms!
Constitutional isomer: the same molecular formula (CH4N2O), yet the constitution (connectivity) of the atoms are different. ! " Different physical properties (e.g. boiling point)!
Structural Theory!
Valence: the number of bonds usually formed by each element! " Predict a structure of organic compounds" ! Atoms that are most commonly bonded to carbon include N, O, H, and halides! (F, Cl, Br, I)! ! With some exceptions, each element generally forms a specic number of ! bonds with other atoms!
Structural Theory!
! Valence: the number of bonds usually formed by each element! " Predict a structure of organic compounds" ! Atoms that are most commonly bonded to carbon include N, O, H, and halides! (F, Cl, Br, I)! ! With some exceptions, each element generally forms a specic number of ! bonds with other atoms!
2 !
Structural Theory!
Structural Theory!
Structural Theory!
Structural Theory!
Structural Theory!
Structural Theory!
3 !
Electrons, Bonds, and Lewis Structures!

Covalent bonding: dened as the result of two atoms sharing a pair of electrons!
Electrons, Bonds, and Lewis Structures!

Covalent Bonding: Internuclear Forces Attractive vs. Repulsive!

Covalent Bonding: Internuclear Forces Attractive vs. Repulsive!

bond length! ! bond strength!
Features of Atomic Structures!

! Protons (+1) and neutrons (electronically neutral) reside in the nucleus! ! Electrons (1) reside outside the nucleus, in shell! ! Some electrons are close to the nucleus and others are far away; quantized! ! Valence electrons: electrons in the outermost shell of an atom ! the number of! valence electrons in an atom is identied by its group number in the periodic ! table! ! Why are valence electrons important?!

! Protons (+1) and neutrons (electronically neutral) reside in the nucleus! ! Electrons (1) reside outside the nucleus, in shell! ! Some electrons are close to the nucleus and others are far away; quantized! ! Valence electrons: electrons in the outermost shell of an atom ! the number of! valence electrons in an atom is identied by its group number in the periodic ! table! ! Why are valence electrons important?!
4 !

! Protons (+1) and neutrons (electronically neutral) reside in the nucleus! ! Electrons (1) reside outside the nucleus, in shell! ! Some electrons are close to the nucleus and others are far away; quantized! ! Valence electrons: electrons in the outermost shell of an atom ! the number of! valence electrons in an atom is identied by its group number in the periodic ! table! ! Why are valence electrons important? Understand structures and properties !
Lewis Structures!
! The Lewis dot structures of an individual atom: the number of valence electrons!
! Electrons (1) reside outside the nucleus, in shell! ! Some electrons are close to the nucleus and others are far away; quantized! ! Valence electrons: electrons in the outermost shell of an atom ! the number of! valence electrons in an atom is identied by its group number in the periodic ! table! ! Why are valence electrons important? Understand structures and properties !
Lewis Structures!
Lewis Structures!
Lewis Structures!
Lewis Structures: CH4!
5 !
Lewis Structures: Octet Rule!
Lewis Structures: NH3!
Octet rule: second-row elements (C,N,O, F) will form the necessary number of bonds so as to achieve the electron conguration of Neoneight valence electrons!
Lewis Structures: Lone Pair!
Formal Charges!
Formal Charges: Associated with any atom that doesnt exhibit the appropriate number of valence electrons. If present in a Lewis structure, the formal charge must be drawn (affecting stability of molecules).! ! To calculate formal charge for an atom: !
Lone pair: unshared or nonbonding electrons!
Compare the number of valence electrons that SHOULD be associated with the atom to the number of valence electrons that are ACTUALLY associated with an atom!
Formal Charges!
Classication of Bonds!
! Covalent bond (p 20)! ! Polar covalent bond! ! Ionic bond! ! by electronegativity! : how strongly an atom attracts shared electrons!
!
!
6 !
Classication of Bonds!
Electronegativity!
! Covalent bond! ! Polar covalent bond! ! Ionic bond! ! by electronegativity! : how strongly an atom attracts shared electrons!
!
!
Electronegativity Differences!
! Electrons tend to shift away from lower electronegativity atoms to higher! electronegativity atoms. ! ! The greater the difference in electronegativity, the more polar the bond.!
Induction (inductive effect)!
< 0.5!
0.5 1.7!
> 1.7!
Atomic Orbitals: Just Background!

! Newtonian classical mechanics vs. Quantum mechanics! ! Classical mechanics doesnt correctly describe the behavior of very small! particles such as electrons and nuclei of atoms and molecules; ! waveparticle duality of matter (and of light)! ! Wave equation: E! = H! (! = wave function, cf. !2 = probability) The solution (energy) to wave equations for electrons provides us with visual ! pictures called orbitals.!
< 0.5!
0.5 1.7!
> 1.7!
! The Heisenberg uncertainty principle states that the more precisely a ! particle's position is known, the less precisely its momentum is known, and vice-! versa. ! "X"Px = h"
7 !
Atomic Orbitals: Just Background!

! Newtonian classical mechanics vs. Quantum mechanics! ! Classical mechanics doesnt correctly describe the behavior of very small! particles such as electrons and nuclei of atoms and molecules; ! waveparticle duality of matter (and of light)! ! Wave equation: E! = H! (! = wave function, cf. !2 = probability) The solution (energy) to wave equations for electrons provides us with visual ! pictures called orbitals.! ! The Heisenberg uncertainty principle states that the more precisely a ! particle's position is known, the less precisely its momentum is known, and vice-! versa. ! "X"Px = h"
Atomic Orbitals: Electronic Density!

! Wave equation: E! = H! (! = wave function, cf. !2 = probability) The solution (energy) to wave equations for electrons provides us with visual ! pictures called orbitals.! ! The Heisenberg uncertainty principle states that the more precisely a particle's position is known, the less precisely its momentum is known, and viceversa. "X"Px = h ! Orbital: a region of space that can be occupied by an electron (!2 = probability)" !
Orbitals: Like a Wave!
Orbitals: Like a Wave!
* nodal plane!
Orbitals!
Filling Atomic Orbitals with Electrons: Three Principles!

! The Aufbau principle: the lowest-energy orbital is lled rst! ! The Pauli exclusion principle: each orbital can accommodate a maximum of two! electrons that have opposite spin" Spin: the electrons intrinsic electromagnetic eld angular momentum! ! ! ! degenerated oribitals! (orbitals with the same energy level) ! ! ! Hunds Rule: For degenerated orbitals (e.g. p orbitals), one electron is placed in! each degenerate orbital rst, before electrons are paired up. !
8 !

! The Aufbau principle: the lowest-energy orbital is lled rst! ! The Pauli exclusion principle: each orbital can accommodate a maximum of two! electrons that have opposite spin" Spin: the electrons intrinsic electromagnetic eld angular momentum! ! ! ! ! ! Hunds Rule: For degenerated orbitals (e.g. p orbitals), one electron is placed in! each degenerate orbital rst, before electrons are paired up. !


Application of Three Principles!

valence electron!
9 !
Quiz 0!
1. Give the ground state electron conguration for magnesium (atomic ! number 12). (5 min)! Answer: 1s22s22px22py22pz23s2 or 1s22s22p63s2!
Quiz 0!
1. Give the ground state electron conguration for magnesium (atomic ! number 12). (5 min)! Answer: 1s22s22px22py22pz23s2 or 1s22s22p63s2!
! !
! !
Nature of Atomic Orbital Overlap: Two Theories!
Valence Bond (VB) Theory!
How is a covalent bond formed from the overlap of atomic overlap?
! Valence bond theory! ! ! Molecular orbital theory! ! ! !
Valence Bond Theory!

A bond: simply viewed as the sharing of electron density between two atoms as a result of the constructive interference of their atomic orbitals.! For example,! ! sigma (#) bond! In fact, all single bond are sigma (#) bond.!
H H H H H H
Valence Bond Theory!

A bond: simply viewed as the sharing of electron density between two atoms as a result of the constructive interference of their atomic orbitals.! For example,! ! sigma (#) bond! In fact, all single bond are sigma (#) bond.!
H H H H H H
10 !
Molecular Orbital (MO) Theory!

Valence bond theory is good, yet not perfect (only use constructive interference). ! Molecular orbitals: mathematically combined atomic orbitals that extend over the ! entire molecule. The mathematical method is called the linear combination of ! atomic orbitals (LCAO).! ! MOs are a more complete analysis of bonds because they include both ! constructive and destructive interference.! ! The number of MOs created must be equal to the number of atomic orbitals that ! were used.! ! H2 MOs!

Valence bond theory is good, yet not perfect (only use constructive interference). ! Molecular orbitals: mathematically combined atomic orbitals that extend over the ! entire molecule. The mathematical method is called the linear combination of ! atomic orbitals (LCAO).! ! MOs are a more complete analysis of bonds ! because they include both constructive and ! destructive interference.! ! The number of MOs created must be equal to! the number of atomic orbitals that were used.! ! This lowering in E is the essence of the bond.! ! H2 MOs (p 22)!

Valence bond theory is good, yet not perfect (only use constructive interference). ! Molecular orbitals: mathematically combined atomic orbitals that extend over the ! entire molecule. The mathematical method is called the linear combination of ! atomic orbitals (LCAO).! ! HOMO (highest occupied molecular orbital):! the highest energy orbital from among the ! occupied orbitals.! ! LUMO (lowest unoccupied molecular orbital): the lowest energy orbital from among ! unoccupied orbitals.! H2 MOs!
He2 ???!
! Draw Molecular Orbitals (MOs) of He2 molecule (atomic number 2). ! ! Why does helium exist in its atomic form rather than in molecular form?! Answer:!
! ! ! ! !
!!
Energy 1s He
Antibonding MO loss of energy 1s He Bonding MO He He (He2) gain of energy
He2 ???!
! Draw Molecular Orbitals (MOs) of He2 molecule (atomic number 2). ! ! Why does helium exist in its atomic form rather than in molecular form?! Answer:!
Hybridized Atomic Orbitals (by Linus Pauling)!
! ! ! ! !
!!
Energy 1s He
Antibonding MO loss of energy 1s He Bonding MO He He (He2) gain of energy
11 !
Hybridized Atomic Orbitals: Excitation (or Promotion)!
Hybridized Atomic Orbitals: Hybridization!

! Hybridization mathematical average of atomic orbitals!
However, the observed three-dimensional geometry! of CH4 is in a perfect tetrahedron.! !
! sp3-hybridized orbitals = 1 s + 3 p orbitals!
!! !
Hybridized Atomic Orbitals!
Ethane!
Double Bonds and sp2 Hybridization$ !
12 !

An sp2 hybridized carbon will have three equal-energy sp2 orbitals and one unhybridized p orbital.!
Double Bonds and sp2 Hybridization: sigma Bond!

sigma Bond: head-on Orbital Overlap!
pi Bond View by Valence Bond Theory!

pi Bond: Side by Side Orbital Overlap!
pi Bond View by Molecular Orbital Theory!

pi Bond: Side by Side Orbital Overlap!
Triple Bonds and sp Hybridization$ !
13 !
Bond Strength and Bond Length$ !
VSEPR Theory: Predicting Molecular Geometry!

Focus on the central atom and count the number of ! bonds and lone pairs. ! Steric number: the number of electron pairs (bonding and nonbonding) that are! repelling each other (the total of ! bonds and lone pairs). ! ! VSEPR theory (valence shell electron pair repulsion): the geometry of the central! atom will be determined by the steric number (minimizing repulsion and ! maximizing distance from electron pairs)! !

Focus on the central atom and count the number of ! bonds and lone pairs. ! Steric number: the number of electron pairs (bonding and nonbonding)! the total of ! bonds and lone pairs (repulsion) ! ! VSEPR theory (valence shell electron pair repulsion): the geometry of the central! atom will be determined by the steric number (minimizing repulsion and ! maximizing distance from electron pairs)! !


14 !
sp3 Molecular Geometry!

For any sp3 hybridized atom, the four valence electron pairs will form a TETRAHEDRAL ELECTRON GROUP geometry.! !



trigonal pyramidal!
trigonal pyramidal!
trigonal pyramidal!


bent!
15 !
sp2 Molecular Geometry: BF3!
Example! ! CH4! ! NH3! ! H2O!
Steric Hybridization! number!

! 4! ! 4! ! 4! ! sp3! ! sp3! ! sp3!
Arrangement of electron pairs!

! Tetrahedral! ! Tetrahedral! ! Tetrahedral!
Arrangement of atoms (geometry)!

! Tetrahedral! ! Trigonal pyramidal! ! Bent!
! Steric number: 3 ! Trigonal planar!
sp2 Molecular Geometry: BF3!

! Steric number: 3 ! Trigonal planar! !
sp Molecular Geometry: BeH2!

! Steric number: 2 ! Linear! !
to a board (p orbial)!
sp Molecular Geometry: CO2 ?!
Summary of Molecular Geometry!
16 !
Dipole Moments and Molecular Polarity!

Dipole moment: used as an indicator of polarity! % Dipole moment = (the amount of partial charge) x (the distance the &+ and &- are separated)! % Dipole moments are reported in units of debye (D); 1 D = 1018 esucm!
% I will skip the calculation of percent ionic character for various bonds.! ! ! Electronegativity differences cause induction ! Induction (shifting of electrons WITHIN their orbitals) results in a dipole ! moment.! ! !

! ! ! ! ! ! ! ! ! ! Note: It is important to determine a molecules geometry rst before analyzing ! its polarity.!
Intermolecular Forces and Physical Properties!

Physical properties of a compound such as solubility, boiling point, density, state of matter, melting point, etc. are affected by the attractions BETWEEN molecules.! ! ! All intermolecular forces are electrostatic (i.e. attraction between opposite ! charges)! ! Neutral molecules (polar and nonpolar) are attracted to one another through:! 1. Dipoledipole interactions! 2. Hydrogen bonding! 3. Dispersion forces (a.k.a. London forces or eeting dipoledipole forces)! ! !

17 !

Intermolecular Forces: 1. DipoleDipole Interactions!

Dipoledipole forces result when polar molecules having permanent dipole moment, line up their OPPOSITE charges.! ! !
Intermolecular Forces: 1. DipoleDipole Interactions!

Dipoledipole forces result when polar molecules having permanent dipole moment, line up their OPPOSITE charges.! ! !
Intermolecular Forces: 2. Hydrogen Bonding!

Hydrogen bonds (H-bonds) are an especially strong type of dipoledipole attraction. Because the partial + and charges are relatively large.! ! ! !
molecular weight: 56 vs. 58 amu!

!% Only when a hydrogen shares electrons with a highly electronegative atom (O, N, F, or Cl) will it carry a large partial positive charge.! % The large &+ on the H atom can attract large & charges on other molecules.! !% Even with the large partial charges, H-bonds are still about 20 times weaker than covalent bonds. [400 kJ/mol (a typical covalent bond) vs. 20 kJ/mol (Hbond)]! !% Compounds with H atoms that are capable of forming H-bonds are called Protic. (e.g. H2O, CH3OH)! ! ! !

18 !

Intermolecular Forces: 2. Hydrogen Bonding in Nature!

C
H N
n
O OH Me
Fmoc
O N R HN H
O N H O R
R
O N
O N H O R HN O
HN
Fmoc
H N
n
O OH Me
HN N H
O
H
N Side-Chain Cross Linking Method: A Hydrocarbon-Stapled Helix
!-Helix
R Main-Chain Hydrogen-Bond Surrogate (HBS): An Artificial !-Helix
Intermolecular Forces: 2. Hydrogen Bonding in Nature!

C
H N
n
Intermolecular Forces: 3. London Dispersion Forces !

!% Hydrocarbons [no permanent dipole moments; nonpolar (dipole = 0 D)] has
O OH Me
Fmoc
O N R HN H
O N H O R
R
O N
O N H O R HN O
weak intermolecular force, where the eeting, or transient, dipole moments exist.!
HN
Fmoc
H N
n
O OH Me
HN N H
O
H
N Side-Chain Cross Linking Method: A Hydrocarbon-Stapled Helix
!-Helix
R Main-Chain Hydrogen-Bond Surrogate (HBS): An Artificial !-Helix
! !

!% Explain why molecules with more mass generally have higher boiling points.! ! ! ! ! !% The greater the surface area of a molecule, the more temporary dipole attractions are possible.!

!% Explain why molecules with more mass generally have higher boiling points.! ! ! ! ! !% The greater the surface area of a molecule, the more temporary dipole attractions are possible.!
! !
! !
19 !
Solubility!
! like dissolves like! ! Polar compounds generally mix well with other polar compounds! !% Nonpolar compounds generally mix well with other nonpolar compounds! !% Soap: amphophilic! ! ! !
Solubility!
Solubility!
20 !

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Organic Chemistry!

! Denition of Organic Chemistry: !

Chapter 1. A Review of General Chemistry! ! "

Structure and Reaction of Organic Molecules!

Structural Theory: Constitutional Isomer!

Lets focus on structure and properties of organic molecules!

Structural Theory: Constitutional Isomer!

Electrons, Bonds, and Lewis Structures!

Electrons, Bonds, and Lewis Structures!

Covalent Bonding: Internuclear Forces Attractive vs. Repulsive!

Covalent Bonding: Internuclear Forces Attractive vs. Repulsive!

bond length! ! bond strength!

Features of Atomic Structures!

Features of Atomic Structures!

Features of Atomic Structures!

Lewis Structures: CH4!

Lewis Structures: Octet Rule!

Lewis Structures: NH3!

Lewis Structures: Lone Pair!

Lone pair: unshared or nonbonding electrons!

Induction (inductive effect)!

Atomic Orbitals: Just Background!

Atomic Orbitals: Just Background!

Atomic Orbitals: Electronic Density!

Orbitals: Like a Wave!

Orbitals: Like a Wave!

Filling Atomic Orbitals with Electrons: Three Principles!

Filling Atomic Orbitals with Electrons: Three Principles!

Filling Atomic Orbitals with Electrons: Three Principles!

Filling Atomic Orbitals with Electrons: Three Principles!

Application of Three Principles!

Application of Three Principles!

Application of Three Principles!

Nature of Atomic Orbital Overlap: Two Theories!

Valence Bond (VB) Theory!

How is a covalent bond formed from the overlap of atomic overlap?

! Valence bond theory! ! ! Molecular orbital theory! ! ! !

Valence Bond Theory!

Valence Bond Theory!

Molecular Orbital (MO) Theory!

Molecular Orbital (MO) Theory!

Molecular Orbital (MO) Theory!

Antibonding MO loss of energy 1s He Bonding MO He He (He2) gain of energy

Hybridized Atomic Orbitals (by Linus Pauling)!

Antibonding MO loss of energy 1s He Bonding MO He He (He2) gain of energy

Hybridized Atomic Orbitals: Excitation (or Promotion)!

Hybridized Atomic Orbitals: Hybridization!

However, the observed three-dimensional geometry! of CH4 is in a perfect tetrahedron.! !

! sp3-hybridized orbitals = 1 s + 3 p orbitals!

Hybridized Atomic Orbitals!

Double Bonds and sp2 Hybridization$ !

Double Bonds and sp2 Hybridization$ !

Double Bonds and sp2 Hybridization$ !

Double Bonds and sp2 Hybridization: sigma Bond!

pi Bond View by Valence Bond Theory!

pi Bond View by Molecular Orbital Theory!

Triple Bonds and sp Hybridization$ !

Triple Bonds and sp Hybridization$ !

Triple Bonds and sp Hybridization$ !

Bond Strength and Bond Length$ !

VSEPR Theory: Predicting Molecular Geometry!

VSEPR Theory: Predicting Molecular Geometry!