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