Naphthenes

Cycloalkanes and Their Derivatives

 Introduction

Naphthenes: cycloparaffins, cycloalkane

Saturated cyclic hydrocarbons

Formula molecules: CnH2n

Examples: cyclopropane, cyclobutane, cyclopentane, cyclohexane

etc

Focus chemicals: cyclopentanes and cyclohexanes

Largely occurring in petroleum, important products

 Production of Naphthenes

20 – 50% from ‘straight run’ gasoline

Problem: boiling points very close to paraffins and aromatic

hydrocarbon, form azeotropes

Straight distillation is not possible to obtain a pure form

1. Requires azeotropic or extraction distillation

2. Dehydrogenation-hydrogenation
Azeotropic / Extraction Distillation
separated from solvent
ex t r ac t io n - s e pa r a t e
un s a tu r a t ed c o m p o u n d s

aniline added to alter the relative

volatilities - separate alkane
Dehydrogenation-Hydrogenation

Dehydrogenation of cyclohexane

Zelinski, before the WWI

T = 300 oC, P = atmospheric, catalyst: Pd or Pt

Hydrogenation of benzene

T = 150 – 200 oC, under pressure to keep in liquid form,

catalyst: Ni

These may be requires absorption or solvent extraction

 Ring Expansion

Ring expansion

Boiled with AlCl3, occurred during cracking process

Equilibrium mixture, 12.5 – 53.5 mole % of methylcyclopentane

Cyclohexane is more stable form at room temperature

Boiling at 65 – 85 oC, isomerised with an AlCl3 complex with trace of

HCl 80 oC, fraction boiling 76 – 85 oC, 88 % cyclohexane

One of the routes to prepare synthetic benzene and derivatives

 Ring Closure

Ring closure
Conversion of the olefin to cyclohexane
T = 550 – 700 oC
Ring closure from paraffin
T = 600 – 700 oC, without catalyst
Lower T, catalyst: chromic oxide
Dehydrogenation
Conversion of the paraffin to an olefin
T ≥ 672 oC, P = atmospheric, 70% conversion
 Ring Enlargement

Rearrangement of methylcyclohexane

More facile than cyclohexane

Higher temperature, more alkylcyclohexane

 Physical Properties

No. of Specific Refractive

Molecular Boiling
Name Carbon Formula Gravity, Index,
Weight Point, oC
Atoms (42 oC) (20 oC)

0.6769 1.3799
Cyclopropane 3 C3H6 42.078 -32.8
(-30 oC) (-42.5 oC)

Cyclobutane 4 C4H8 56.104 0.6997 12.5 1.365

Cyclopentane 5 C5H10 70.130 0.7505 49.3 1.40645

Cyclohexane 6 C6H12 84.156 0.7834 80.1 1.42623

Cycloheptane 7 C7H14 98.182 0.8157 118.8 1.4449

Cyclooctane 8 C8H16 112.208 0.8405 151.1 1.4587

Cyclononane 9 C9H18 126.234 0.8545 178.4 1.4666

 Linear vs Cyclic
Cyclopentane n-pentane Cyclohexane n-hexane
No. of C Atoms 5 5 6 6

Formula C5H10 C5H12 C6H12 C6H14

Molecular
70.13 72.15 84.16 86.17
Weight
Specific Gravity,
0.7505 0.6312 0.7834 0.6640
(42 oC)
Boiling Point, oC 49.3 36.1 80.1 68.7
Refractive Index,
1.40645 1.35748 1.42623 1.37486
(20 oC)
Aniline Point, oC 17.5 71.6 30.0 69.2

Aniline point: the lowest temperature (°F or °C) at which equal volumes of
aniline (C6H5NH2) and the oil form a single phase. The aniline point (AP)
correlates roughly with the amount and type of aromatic hydrocarbons in an oil
sample.
 Summary

 Production by azeotropic/extraction distillation – impurity

regarding to the similar boiling point

 Dehydrogenation-Hydrogenation - Thermal and catalyst

 Ring closure – thermal condition, from paraffin and olefin

 Ring enlargement – ethylcyclopentane

 Comparison between naphthenes and paraffin