Organic Chemistry
By
Ismono
Jurusan Kimia FMIPA UNESA
2016
RENCANAPEMBELAJARANSEMESTER(RPS)
IdentiasMataKuliah
ProgramStudi :Kimia
NamaMataKuliah :KimiaOrganikI
SKS :3
Prasyarat : Telah menempuh matakuliah Kimia Dasar II.
DosenPengampu :ProfDr.Suyatno,M.Si
Dra.NurulHidayati,M.Si.
Drs.Ismono,M.S.
Deskripsi :
Kajian pengetahuan tentang teori struktur, rumus, hibridisasi, tata nama,
isomer, sifat-sifat senyawa organik golongan hidrokarbon alifatik (alkana,
alkena, alkuna), alisiklik, aromatik, alkil halida, dan dasar-dasar stereokimia,
senyawa alkohol fenol, dan aldehid keton, serta pembekalan keterampilan,
sikap ilmiah, kerjasama, dan kemampuan berkomunikasi melalui kajian teori
struktur kimia organik. Untuk mencapai capaian pembelajaran digunakan
metode tanya-jawab, diskusi, kerja kelompok, dan peneylesaian soal-soal
Referensi :
1.Fessenden and Fessenden. 1992. Kimia Organik Jilid I.
Jakarta: Erlangga.
2.Fessenden and Fessenden. 1992. Kimia Organik Jilid II.
Jakarta: Erlangga
3.Robert V, Hoffman, 2004, Organic Chemistry, an Intermediate
Text, Second Adition, Canada, John Wiley and Sons. Inc.
Publications,
4.Solomons G., TW. 1996. Organic Chemistry sixth edition.
New York: John Wiley & Sons Inc.
5.Hardjosudirdjo, W., dkk. 1990. Diktat Kimia Organik I.
Proyek Pengembangan Perguruan Tinggi Bantuan Luar Negeri.
Yogyakarta.
6.Artikel dalam jurnal terkait yang dapat ditelusuri melalui webb .
Chapter 1. Atomand
Molecule
Structure and Bonding
OrganicChemistry
Organic until mid 1800s referred to
compoundsfromlivingsources(mineral
sources were inorganic)
Whler in 1828 showed that urea, an organic
compound, could be made from a non-living
source:
13
ORGANICCHEMISTRY
The study of carbon-containing compounds.
Organic compounds contain backbones
comprised of chains and/or rings of carbon and
hydrogen atoms.
Commonly used formulas are empirical,
molecular, structural (bond-line, condensed and 3-
D), which are most commonly used over
empirical, molecular formulas.
OrganicChemistry
Today, organiccompounds are those
based on carbon structures and organic
chemistry studies their structures and
reactions:
Includesbiologicalmolecules, drugs,
solvents, dyes, food additives,
pesticides, and others.
Does not include metal carbonate salts
and other simple ionic compounds
(inorganic)
Na2CO3, CaCO3, MgCO3, et al
15
HYDROCARBONS
Compounds composed of only carbon and hydrogen atoms (C,H).
Acyclic (without rings); Cyclic (with rings); Saturated: only carbon-carbon
single bonds; Unsaturated: contains one or more carbon-carbon double and/or
triple bonds
They represent a backbone when other heteroatoms (O, N, S, .....) are
substituted for H. (The heteroatoms give function to the molecule.)
Consider the bonding arrangements for (C, H, O, and N). Particularly that
each carbon has 4 bonds.
Sifat-sifat senyawa
pada implementasi
dalam kehidupan
sehari-hari
18
Thebasicstructureoftestosterone(malehormone)
andestradiol(femalehormone)isidentical.
Botharesteroidswithfourfusedcarbonrings,
buttheydifferinthefunctionalgroupsattached
totherings.
Thesetheninteractwithdifferenttargets inthe
body.
Fig.4.8
Copyright2002PearsonEducation,Inc.,publishingasBenjaminCummings
mirror
plane
OH OH
H CH3 CH3 H
HO 2C CO 2H
(S)(+) lactic acid (R)(-) lactic acid
from muscle tissue
o
from milk o
[] = +13.5 [] = -13.5
observed rotation
rotation of pure enantiomerx 100 = enantiomeric excess (e.e.)
o
observed rotation = +109
109.0
e.e. = 123.0 x 100
= 88.6% e.e.
H H
88.6% (+)
(S)-(-) Limonene (R)(+) Limonene 11.4% racemic
o o
[= [] = +123.0 actually 94.3% (+)
from lemons from oranges
Organic Chemistry
25
The Nature of the Chemical
Bond
Atoms form bonds because the compound
thatresultsismorestablethanthe
separateatoms
Ionic bonds in salts form as a result of electron
transfers
Organic compounds have covalent bonds from
sharing electrons (G. N. Lewis, 1916)
26
The Nature of the Chemical
Bond
Lewisstructures shown valence electrons of
an atom as dots
Hydrogen has one dot, representing its 1s
electron
Carbon has four dots (2s2 2p2)
Stable molecule results when the outermost
(valence) shell is completed: octet(eight
dots) for main-group atoms (two for hydrogen)
27
NumberofCovalentBondstoan
Atom
Atoms with one, two, or three valence
electrons form one, two, or three bonds
Atoms with four or more valence electrons
form as many bonds as they need electrons to
fill the sandplevelsoftheirvalence
shellstoreachastableoctet
28
29
NumberofCovalentBondstoan
Atom
30
ValencesofCarbon
Carbon has four valence electrons (2s2 2p2),
forming four bonds (CH4)
31
ValencesofOxygen
Oxygen has six valence electrons (2s22p4) but forms
two bonds (H2O)
s
sp3
sp3 sp3
32
ValencesofNitrogen
Nitrogen has five valence electrons (2s22p3)
but forms only three bonds (NH3)
33
Non-bondingelectrons
Valence electrons not used in bonding are called
nonbondingelectrons, or lone-pairelectrons
Nitrogen atom in ammonia (NH 3) Shares six valence
electrons in three covalent bonds and remaining two
valence electrons are nonbonding lone pair
34
Somesimplemolecules:
35
Valence Bond Theory
Covalent bond forms when two
atoms approach each other closely
so that a singly occupied orbital on
one atom overlaps a singly occupied
orbital on the other atom
36
Valence Bond Theory
Electrons are paired in
the overlapping orbitals
and are attracted to
nuclei of both atoms
HH bond results from the
overlap of two singly
occupied hydrogen 1s
orbitals
H-H bond is cylindrically
symmetrical, sigma()
bond
37
Bond Energy
Reaction 2 H H2 releases 436 kJ/mol
Product has 436 kJ/mol less energy than two
atoms: HH has bondstrength of 436 kJ/mol
38
Bond Length
Distance between
nuclei that leads to
maximum stability
If too close, they
repel because both
are positively
charged
If too far apart,
bonding is weak
39
What is a Bond? An Energy
Minimum
40
Hybridization:sp3 Orbitals
andtheStructureof
Methane
Carbon has 4 valence electrons (2s2 2p2)
In CH4, all CH bonds are identical (tetrahedral)
sp3hybridorbitals:sorbitalandthreep
orbitalscombinetoformfourequivalent,
unsymmetrical, tetrahedral orbitals (sppp =
sp3), Pauling (1931)
41
sp3Hybridization
42
TetrahedralStructureof
Methane
sp3orbitalsonCoverlapwith1s
orbitalson4Hatomtoformfour
identicalC-Hbonds
Each CH bond has a strengthof438
kJ/molandlengthof110pm
Bondangle:each HCH is 109.5,the
tetrahedral angle.
43
TetrahedralStructureof
Methane
44
Tetrahedral Carbon:
45
Hybridization: sp3 Orbitals and
the Structure of Ethane
Two Cs bond to each other by overlap of
an sp3 orbital from each
Three sp3 orbitals on each C overlap with H
1s orbitals to form six CH bonds
46
Hybridization: sp3 Orbitals and
the Structure of Ethane
CH bond
strength in
ethane 420 kJ/mol
CC bond is 154
pm long and
strength is 376
kJ/mol
All bond angles of
ethane are
tetrahedral
47
Hybridization: sp2 Orbitals and
the Structure of Ethylene
48
Hybridization:sp2 Orbitals
andtheStructureof
Ethylene
sp2hybridorbitals:
2sorbitalcombines
withtwo2porbitals, 90
120
giving3orbitals(spp
=sp2)
sp2orbitalsareina
planewith120
angles
Remaining p orbital is
perpendicular to the
plane
49
BondsFromsp2Hybrid
Orbitals
Two sp2-hybridized orbitals overlap to form a bond
p orbitals overlap side-to-side to formation a pi()
bond
sp2sp2 bond and 2p2p bond result in sharing
four electrons and formation of C-C double bond
Electrons in the bond are centered between nuclei
Electrons in the bond occupy regions are on either
side of a line between nuclei
50
BondsFromsp2Hybrid
Orbitals
51
StructureofEthylene
Hatomsformbondswithfoursp2orbitals
HCHandHCCbondanglesofabout120
CCdoublebondinethyleneshorterand
strongerthansinglebondinethane
EthyleneC=Cbondlength133pm(CC154
pm)
52
Hybridization:sp Orbitals
andtheStructureof
Acetylene
C C a triple bond sharing six electrons
53
Hybridization:sp Orbitals
andtheStructureof
Acetylene
Carbon 2s orbital hybridizes with a single p orbital
giving two sp hybrids (two p orbitals remain unchanged)
sp orbitals are linear, 180 apart on x-axis
Two p orbitals are perpendicular on the y-axis and the z-
axis
54
OrbitalsofAcetylene
Two sp hybrid orbitals from each C form spsp bond
pz orbitals from each C form a pzpz bond by
sideways overlap and py orbitals overlap similarly
55
BondinginAcetylene
Sharing of six electrons forms C C
Two sp orbitals form bonds with hydrogens
56
ComparisonofC-C&C-H
bonds:
57
ComparisonofC-Hbonds:
Energy Length
Molecule CharacsBond
(kcal) (pm)
Ethane 25% C(sp3)-H 100 110
33,3% C(sp2)-
Ethylene 106 108
H
Acetylen
e 50% C(sp)-H 132 106
58
ComparisonofC-Cbonds:
Energy Length
Molecule ChartsBond
(kcal) (pm)
25 % C(sp3)-
Ethane
(sp3) 90 154
33,3% C(sp2)-
Ethylene
C(sp2) 146 133
50% C(sp)-
Acetylene
C(sp) 200 120
59
HybridizationofNitrogen
andOxygen
Elements other than C can
have hybridized orbitals
HNHbondanglein
ammonia(NH3)107.3
Ns orbitals (sppp) hybridize
to form four sp3 orbitals
Onesp3orbitalisoccupied
bytwononbonding
electrons,andthreesp3
orbitalshaveoneelectron
each,formingbondstoH
60
HybridizationofOxygenin
Water
The oxygen atom is sp3-hybridized
Oxygen has six valence-shell electrons but forms
onlytwocovalentbonds,leavingtwolone
pairs
TheHOHbondangleis104.5
61
MolecularOrbitalTheory
A molecular orbital (MO): where electrons are
most likely to be found (specific energy and
general shape) in a molecule
BondingMO is formed by the additive
combination of atomic orbitals (lower in energy)
AntibondingMO is formed by the subtractive
combination of atomic orbitals (higher in
energy)
62
MolecularOrbitalTheory
63
MO for H2type
molecules: H2+, H2, H2,
He2+
Generalize the technique of LCAO
Theories of chemical bonding 64
Ethane
65
MolecularOrbitalsin
Ethylene
The bonding MO is from combining p
orbital lobes with the same algebraic sign
The antibonding MO is from combining
lobes with opposite signs
Only bonding MO is occupied
66
MO Ethene
(ethylene)
67
MolecularOrbitalsin
Ethylene
68
Summary
Organicchemistry chemistry of carbon compounds
Atom: positively charged nucleus surrounded by
negatively charged electrons
Electronic structure of an atom described by wave
equation
Electrons occupy orbitals around the nucleus.
Different orbitals have different energy levels and different
shapes
s orbitals are spherical, p orbitals are dumbbell-shaped
Covalentbonds - electron pair is shared between
atoms
69
Summary
Valencebondtheory-electron sharing occurs
by overlap of two atomic orbitals
Molecularorbital(MO)theory, - bonds result
from combination of atomic orbitals to give
molecular orbitals, which belong to the entire
molecule
Sigma()bonds - Circular cross-section and are
formed by head-on interaction
Pi()bonds dumbbell shape from sideways
interaction of p orbitals
70
Summary
Carbonuseshybridorbitalstoformbondsin
organicmolecules.
In single bonds with tetrahedral geometry, carbon
hasfoursp3hybridorbitals
Indoublebondswithplanargeometry,carbonuses
three equivalent sp2 hybrid orbitals and one
unhybridizedporbital
Carbon uses two equivalent sp hybrid orbitals to
form a triple bond with linear geometry, with two
unhybridizedporbitals
Atoms such as nitrogen and oxygen
hybridizetoformstrong,orientedbonds
The nitrogen atom in ammonia and the oxygen
atominwateraresp3-hybridized
71
