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CHEM 103

Ch. 1
Hydrocarbons!
Molecular Name Molecular Name
Formula Formula
CH4 methane C6H14 hexane
C2H6 ethane C7H16 heptane
C3H8 propane C8H18 octane
C4H10 butane C9H20 nonane
C5H12 pentane C10H22 decane

IUPAC Common IUPAC Common


Name Name
butane n-butane 2-methyl butane isopentane
2-methyl isobutene 2,2-dimethyl neopentane
propane propane
pentane n-pentane 2,4-dimethyl n/a
hexane

Properties of Alkanes:

# of Physical
Carbons State
1-4 gas
5-17 liquid
18 solid

Density < 1 g/mL


Insoluble in H2O
Complete combustion in excess O2
heat

o Alkane + O2 spar CO2 + H2O
k
Substitution
o Chlorination of Methane:

CH4 + Cl2 CH3Cl + HCl


CH2Cl2 + 2HCl
CHCl3 + 3HCl
CCl4 + 4HCl

Halogenated Hydrocarbons
o CF3CCl2H (Halothane)
1,1,1-trifluoro-2-bromo-2chloro ethane

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non-flammable
toxic

Cycloalkanes

Cyclopropane 49

Cyclobutane
90

Cyclopentane
108

Cyclohexane
109

Alkenes:
Formula: CnH2n
Has at least one carbon-carbon double bond
Naming
o Choose the longest carbon chain which contains the double
bond
o Number from the end closest to the double bond
Cis-Trans Isomerism
o Physical properties (BP, density, etc.) of cis and trans
isomers differ
Physical properties similar to alkanes
o Density < 1g/mole
o Insoluble in H2O
Chemical properties
o Addition
Hydrogen
Halogens
Hydrogen Halide
o HBr, HCl, etc.

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o Combustion

Molecular Formula IUPAC Common Name


CH2=CH2 ethene ethylene
CH2=CHCH3 1-propene propylene
CH2=CHCH2CH3 1-butene
CH3CH=CHCH3 2-butene
CH2=CCH3 2-methyl-1-propene
CH3

Alkynes
Formula: CnH2n-2
Has at least one carbon-carbon triple bond
Naming
o Choose the longest carbon chain which contains the triple
bond
o Number from the end closest to the triple bond
Physical properties similar to alkanes and alkenes
Chemical properties similar to alkenes

Molecular Formula IUPAC Common Name


HC CH ethyne acetylene
HC CCH3 1-propyne
HC CCH2CH3 1-butyne
CH3C CCH3 2-butyne

Aromatics
Benzene

+ Br-Br bromocyclohexane (slow substitution


reaction)
Cyclohexan
e

+ Br-Br 1,2-dibromocyclohexane (fast addition


reaction)
Cyclohexen
e
Benzen
+ Br-Br
e bromobenzene (slow substitution
reaction)

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Benzene is also pictured as because it has a resonance
structure.

Aromatic Compounds

Toluene (methylbenzene)

Chlorobenzene

ortho-xylene meta-xylene para-


xylene

1,4-dichlorobenzene (para-dichlorobenzene)

1-chloro-2-methylbenzene
(ortho-chlorotoluene or 2-chlorotoluene)

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Physical properties similar to other hydrocarbons
o Liquid (6 carbon atoms)
Chemical properties
o Substitution
Halogens
Nitric Acid
Nitrobenzen
e

2,4,6-trinitrotoluene (TNT)

2,4,6-trinitro-methylbenzene?

Petroleum
Straight chain n-alkanes
Some branched near the ends

Catalytic Cracking 1-4 Carbons


Used to break down longer
carbon chains into shorter
carbon chains 5-12 Carbons

13-15 Carbons
Octane Number of a gasoline: %
isooctane in an isooctane-heptane
mixture that gives the same 15-17 Carbons
performance of the gasoline

Name Formula Octane


18+ Carbons Number
n-octane CH3(CH2)6CH3 -18
n-heptane CH3(CH2)5CH3 0

5
2,2-dimethylbutane (CH3)3CCH2CH3 94
2,2,4- 100
trimethylpentane
isooctane
benzene 101

toluene 112

ethanol CH3CH2OH 116

Compounds with high O.N.


Highly-branched alkanes
Aromatic (benzene derivative)
Alcohol

Catalytic Converter
Finely divided metal (Pd or Pt)
Pd
2CO + O2 2CO2
Pd
CnH2n+2 CO2 + H2O
Unburned

Increase O.N. by adding anti-knock agents


Soluble in gasoline
Cheap
Cannot be toxic or otherwise bad for the environment or bad for
the catalytic converter (see tetraethyl lead)
Primary
Alcohols
General Formula: R OH
3 types Secondary
o Primary
o Secondary
o Tertiary Tertiary
Physical properties
o Boiling Point
Hydrogen bonding causes higher BPs than in Alkanes of
similar size
o Solubility
Alcohols with <5 carbons are water soluble
Molecular Formula IUPAC Common Name
CH3OH methanol methyl alcohol
CH3CH2OH ethanol ethyl alcohol
CH3CH2CH2OH 1-propanol n-propanol

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CH3CHCH3 2-propanol isopropanol
OH isopropyl alcohol
(rubbing)
HOCH2CH2OH 1,2-ethanediol ethylene glycol
1,2-dihydroxy ethane
HOCH2CHCH2OH 1,2,3-propanetriol glycerol
OH 1,2,3- glycerine
trihydroxypropane
hydroxybenzene phenol

Alcohol Oxidization
Oxidization agent
o KMnO4
o K2Cr2O7
Primary alcohols oxidize to aldehydes
Secondary alcohols oxidize to ketones
Tertiary alcohols do not oxidize

Phenols
Phenols are easily oxidized to give a mixture of products
Phenol is a weak acid
o Ka 10-10

Ethers
Formed when two alcohols react
o ROH + HOR R O R + H2O

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Physical Properties
o Boiling Point
o Solubility
5 Carbons are water soluble
Chemical Properties
o Ethers oxidize to form peroxides

Molecular IUPAC Common Name


Formula
CH3CH2OCH2CH3 diethyl ether
CH3CH2OCH3 ethyl methyl ether
methyl phenyl ether anisole

methoxybenzene

2-butyl-4- butylated
methoxybenzene hydroxyanisole

Aldehydes and Ketones


Aldehyde Formula: Ketone Formula:

Physical Properties
o BP
o Solubility
Chemical Properties
o Oxidation (aldehydes only) to a carboxylic acid
o Aldehydes reduce to a primary alcohol
o Ketones reduce to a secondary alcohol
o Aldehydes react with alcohols to form the unstable
hemiacetal

The hemiacetal then becomes an acetal

o Aldehydes react with alcohols to form the unstable


hemiketal

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The hemiketal then becomes a ketal

Molecular IUPAC Common Name


Formula
methanal formaldehyde

ethanal acetaldehyde

propanal propionaldehyde

2-hydroxybutanal -
hydroxybutyraldehyd
e
benzaldehyde

4-hydroxy-3- vanillin
methoxybenzaldehyde

propanone acetone

2-butanone methylethylketone
(MEK)
acetophenone

benzophenone

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butyrophenone

Carboxylic Acids
General Formula:

Physical Properties
o Solubility
<5 Carbons are water soluble
o Boiling Point
Unusually high due to hydrogen bonding
Chemical Properties
o Weak Acids
Neutralize to form a salt and water
Naming salts
Name the cation, and then write the name of
the anion with the ending oate

Potassium Sodium benzoate


ethanoate

Molecular Formula IUPAC Common Name


methanoic acid formic acid

ethanoic acid acetic acid

butanoic acid butyric acid

benzoic acid

2-hydroxybenzoic acid salicylic acid

4-aminobenzoic acid

2-hydroxypropanoic lactic acid


acid

2-aminopropanoic acid alanine

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octadecanoic acid stearic acid

Esters
General Formula:

Form when a carboxylic acid reacts with an alcohol


(esterification)
Physical Properties
o Pleasant smell
o Solubility
<5 Carbons are water soluble
o Boiling Point
No hydrogen bonding
Comparable to aldehydes, ethers, and ketones
Chemical Properties
o Hydrolysis
Acid-catalyzed
Yields an acid and an alcohol
Reversible
Base-catalyzed
Yields a salt and an alcohol
Irreversible

Molecular Formula IUPAC Common Name


ethyl methanoate ethyl formate

ethyl heptanoate

octyl ethanoate octyl acetate

methyl salicylate (wintergreen)

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Amines
General Formula:

Physical Properties
o Boiling Point
Primary and secondary have high BPs but not tertiary
o Solubility
<5 carbons are water soluble
Chemical Properties
o Ionization
NH3 + H2O NH4+ + OH-
RNH2 + H2O RNH3+ + OH-
R2NH + H2O R2NH2+ + OH-
R3N + H2O R3NH+ + OH-
o Neutralization
NH3 + HCl RNH2 HCl
RNH3 + HCl RNH2 HCl
R2NH + HCl RNH2 HCl
Molecular Formula IUPAC Common Name
methyl amine

dimethyl amine

ethyl dimethyl amine

1,6-hexanediamine 1,6-diaminohexane
aminobenzine aniline

1-amino-2-
phenylethene
1-phenyl-2- amphetamine
aminopropene

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methamphetamine

1-phenyl-2- P2P
hydroxypropane

Amides
General Formula:

carboxylic acid amine amide


Physical Properties
o Boiling Point
Unusually high due to hydrogen bonding
o Solubility
<5 carbons are water soluble
Chemical Properties
o Hydrolysis

o Neutral

Molecular Formula IUPAC Common Name


methanamide formamide

ethanamide acetamide

Thiols (Mercaptans)
General Formula: R-S-H

Molecular Formula IUPAC Common Name


methanethiol methyl mercaptan

propanethiol propyl mercaptan


(onions)
t-butyl mercaptan (natural gas additive)
isobutyl mercaptan (skunks)

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Nitriles (Cyanides)
General Formula:

Molecular Formula IUPAC Common Name


cyanomethane methyl cyanide

Addition Polymers
Made by adding monomer units (usually containing C=C)
directly together
Pressure (1000-3000
o n CH2=CH2 Heat (100-250C)
atm)

Polyethylene
o Polypropylene

o Polystyrene

polyphenylethene
Not reactive
o Polyhalogenated Alkenes
Vinyl Chloride

Vinyl Chloride Polyvinyl Chloride (PVC)

Poly-tetrafluoroethene (Teflon)

Poly-1,1-dichloroethene (Saran)

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Polyethylene terephthalate (Dacron)

High-density polyethylene (linear)

Polyvinyl Chloride (PVC)

Low-density polyethylene (branched)

Polypropylene

Polystyrene

Hot Dog

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Acrylics
o Acrylic acid Polyacrylic acid

o Methacrylic acid Polymethacrylic acid

o Methyl methacrylate Polymethyl methacrylate


(PMMA)

o Polyisoprene
Isoprene

Poly-cis-isoprene (Natural Rubber)

Poly-trans-isoprene (brittle)
Vulcanization
Vulcanized natural rubber is used for tires

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Condensation Polymers
Monomer units (usually containing different functional groups)
combine to lose a small molecule (HCl, H2O)
Polyesters
o Alcohol + carboxylic acid ester + H2O
o Diol + dicarboxylic acid polyester + H2O
Ethylene glycol + terephthalic acid
polyethylene
terephthalate

Polyamide
o Primary amine + Carboxylic acid amide + H2O
o Diamine + diacid polyamide (nylon) + H2O

o Nylon A, B
A is the number of carbons in the diamine
B is the number of carbons in the diacid

Polymers in general
Molecular weight
o M = n mo

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n is the degree of polymerization
mo is the molar mass of the repeated unit
o Weight must be at least 10,000 before the polymer
becomes useful

n M Physical State
1 1(28) = 28 gas
2 2(28) = liquid
4 4(28) = liquid
100 100(28) = 2800 solid
200 200(28) = 5600 solid
10,000 resin (plastic) / useful
polymer

Temperature Transitions
o Glass transition temperature, Tg , comes before the melting
point, Tm
o polymer (s) polymer (s) polymer (l)
Brittle Tg flexible Tm
liquified

Polymer Repeat Unit Tg Tm


polyethylene ~CH2CH2~ -120 137
polypropylene -18 176

polystyrene 100 240

teflon ~CF2CF2~ 126 327


nylon 6,6 50 265

Isomerism
Structural isomers
o Same molecular formula, but different connectivity

1-propanol 2-propanol
methoxyethane
Geometric isomers
o Same molecular formula, same connectivity, but different
arrangements in space

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o Cis-trans isomerism
Optical Isomerism
o Achiral can superimpose mirror images
o Chiral cannot superimpose mirror images
Asymmetric C carbon bonded to 4 different atoms
or groups of atoms

o Rotation of polarized light


Enantiomers are optical isomers which rotate
polarized light in opposite directions
(+) d dextrorotary: rotates light clockwise
() l levorotary: rotates light counterclockwise
which is which must be determined by
experimentation
ex. Limonene:

o Fischer projections
Chiral carbon goes in the middle
When the heavier group is on the left, its the L-
enantiomer
When the heavier group is on the right, its the D-
enantiomer
Glyceraldehyde

L-glyceraldehyde D-glyceraldehyde
(-) (+)

Carbohydrates
Monosaccharides
o Cn(H2O)n
o Aldoses hydroxy aldehydes
v
H H H H
C=O C=O C=O C=O

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CHOH CHOH CHOH CHOH
CH2OH CHOH CHOH CHOH
CH2OH CHOH CHOH
CH2OH CHOH
CH2OH

aldotriose aldotetrose aldopentose aldohexose

o Ketoses hydroxy ketones

CH2OH CH2OH CH2OH CH2OH


C=O C=O C=O C=O
CH2OH CHOH CHOH CHOH
CH2OH CHOH CHOH
CH2OH CHOH
CH2OH

ketotriose ketotetrose ketopentose ketohexose

o Aldotetroses

D-aldotetrose L-aldotetrose D-aldotetrose L-aldotetrose

o Aldopentoses

D- D- D- D- L- L- L- L-
ribose

Cyclic Sugars
o D-aldohexose (straight chain) cyclic hemiacetal

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-D-aldohexose -D-aldohexose
-D-glucose -D-glucose
#1 is the anomeric carbon
o Reactions
Oxidation
Aldoses and Ketoses oxidize to carboxylic acids
Any sugar (except sucrose) can be oxidized
Formation of Ethers
2 sugars disaccharide

-D-glucose + --D-glucose maltose (-1,4-linkage)


-D-glucose + --D-glucose cellobiose (-1,4-
linkage)
-D-galactose + --D-glucose lactose (milk sugar)
-D-glucose + -D-fructose sucrose (table sugar) (--
linkage)
-D-glucose polymer starch (amylose) (-1,4-
linkage)
-D-glucose polymer cellulose (-1,4-linkage)
cellulose soaked in HNO3 and nitrocellulose
H2SO4
Lipids
Soluble in nonpolar solvents (benzene, CCl4)
Fats
o Glycerol + 3 fatty acids triester / triglyceride / fat
o Fatty acid
Even number of carbons
Straight chain
Usually long chain

Molecular Formula IUPAC Common Name


hexadecanoic acid palmitic acid
octadecanoic acid stearic acid

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Contains no C-C double bonds
Saturated fatty
acid
Contains C-C double bonds Unsaturated fatty
acid
Oleic acid

Omega-3 fatty acid


The first C-C double bond is 3 carbons from the
end
COOH-CH=CHCH2CH2CH2CH=CHCH2CH3
Hydrogenation
Double bonds are reduced to single bonds
Oxidation
Results in a rancid mixture of ketones,
aldehydes, and acids (double bonds are
reactive)
Antioxidant food additives prevent oxidation of
fats
Saponification
Base-catalyzed hydrolysis
Breaks fats back into glycerol and 3 sodium or
potassium salts (soaps)

Soaps break dirt into micelles which are then


washed away by water

3 types of soaps
o anionic
o cationic
o nonionic (in green cleaners)
o Soaps/Detergents
Carboxylates
Bar soap

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Ex. Sodium Stearate
Not always soluble in water
Sulfonates
Shampoo soap
Ex. Sodium Sulfonate
Soluble in water
o Steroids
Testosterone
One ketone group
Anabolic

Androstenedione
Two ketone groups
Nonanabolic

1-methyl-3-oxoandrost-1-en-17-ylacetate
Ester group
Anabolic
Testing for testosterone
The normal ratio for testosterone (T) to
epitestosterone (E) is about 1T:1E. A ratio of
>6T:1E is illegal in sporting competitions.

Proteins
Polyamide polymers built from amino acids

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Amino Acid

R-group Name (abb)


H glycine (gly)
CH3 alanine (ala)
CH2CH2COOH glutamic acid (glu)
(MSG)

Isomers of Alanine (2-aminopropanoic acid)


o D-Alanine
o L-Alanine
Dipeptides
o Two amino acids joined by a peptide bond
o Structure and activity are not related
o ex. aspartic acid (asp) + phenylalanine (phe) asp-phe
o ex. phenylalanine (phe) + aspartic acid (asp) phe-asp
Aspartame is the methyl ester of phe-asp

Pentapeptides
o Five amino acids joined by peptide bonds
o Structure and activity are related
Certain structural features occupy certain receptor
sites

Morphene Codeine
similar structural features - both are used as painkillers

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Polypeptides
o ex. Insulin (51 amino acids)
o ex. Human Growth Hormone (HGH) (191 amino acids)

Soluble in water? Examples


Operational Yes enzymes, hormones
Structural No hair, skin

o Structure - Proteins
1. Primary
Sequence of amino acids
2. Secondary
H-bonding between peptides
helix (most common)
pleated sheet
3. Tertiary
Interaction between side (R) groups
4. Quaternary
Aggregation > 1 protein molecule
ex. 4 hemoglobin molecules
o Hydrolysis of peptides
1. HCl
HCl
-ala-gly-asn-glu-ala- 2 ala + gly + glu +
asp
Most amino acids remain intact with HCl
HCl attacks amide linkage:
o Gln Glu
o Asn Asp
2. Enzyme
Selecive
enzyme
-ala-gly-asn-glu-ala- ala-gly + asn-glu-
ala

Nucleic Acids
Genetic material

-D-ribose -D-2-deoxyribose
(RNA) (DNA)

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Adenine Cytosine Guanine Thymine Uracil
(DNA only) (RNA only)

Phosphate linkage

Base pairs
o Adenine pairs with Thymine

o Cytosine pairs with Guanine

DNA RNA
Sugar: -D-2-deoxyribose -D-ribose
N Bases: AGCT AGCU

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Backbone: Phosphate linkage
Secondary Structure: Double-helix Usually single-
stranded
Replication

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