~ king _

It is defined as the n1etallic s~ nd,3imilar to rattling of hammer produced in internal combust10 n

e·ngine due to immature ignition of fuel air mixture. _ .
' An internal combustion engine uses eit her gasoline or diesel as fuel. ln internal combustion
engine, a mixture of fuel (gasoline or diesel) is ignited in a cylinder . The ignition is brought about
by means of an electric spark (in petrol engines) or by cornpressing the air (in diesel engines) .
The gases evolved during ignition, force the pisto n do\vn due to high pressure thus producing
~ ical structure and knocking
-
1. The knocking tendency decreases with increase in compactness of the molecule.
/ Knocking decreases with the increase in the number of double bonds and rings (cyclic struc-
ture).
3. With normal paraffins, the k1;ocking_increases with increase in length of the hydrocarbon
chain. Thus, the knocking t~hdency increases from n-butane to n-heptane. -

----
t
- ;a.._

,. tnr ( k.1 "'a '1 J~ I,~) 'i. 'h.'rwd) .

-- I I - - ·" ll<-: i . ~ . - ~~ ·

Fuel< • 47
.r ·1,...

,.,. .
:'

Oll r.111 .- It t ..'i,. I.J. l'

II

-
<. 11 / 1<' 1ll.l! k ' <. 11

·- k11 0,k 111~ inu c., ·,n -

<.. I I

__
IH ' J> L II I<.'
. ,.
'~·
.
7✓
4. 1':11 0 , ki 11g J cu e.uc ~ ·~·' !:1c _l>1 .rn ~h ing_J1 1 ca rbon d1 ai 11 i11 crc,1.~cs.
ll li q>t.mt· > 2 rn cr! ,ylh cx·rnc > 2 2 , . . I I -- - - - - t .(
• • -u1mc1 1y p c 111 a n c
- - - - knoc k ing decreases - - - ~ ,,..
5. /\rt1m a 1ic< such as benzene and tul .I I. _
uenc iave very 11gh antiknock properties. f,.
~11 gc n(-ral d_
1e tendency of fuel constituents to knock is in the followin order
Straig ht cl1:1111 paraffins> branched chain ffi . . g
(1.c., naphthalenes) > aromatics. . para Ills (1.e. , isoparaffins) olefins > cycloparaffins

~ ,ne rating
: In order to classify the fuels according to their kno ki · b"
Ed . I 926 kn c ng property, an ar maty scale was provided by
- ger 111 , • own as octane rating or octane number: It is observed th t h kn ks r
badly; hence. it was arbitrarily assigned an antiknock val.ue of O ha n-theptahned ~c very (.

-;;---- . . . zero . n t e o er an , 1sooctane

•.(2-r=,- ,4-tnmethy!pentane)
f =::::::::==== has a high_ resistance
_ to knocking and h ence was arb'1tran·1y ass1gne
'" · d a
vaiue o 100 . · -

CH3 H
I I H H H H H H H
I : I I I I I
CH3 -C-CH,-C-CH3
· I - I H- C - C - C - C - C - C - C- H
I I I I I I I
CH3 CH3 H H H H H H H
Isooctane n-heptane
2,2,4-trimethylpencane (Octane number 0)
(Octane number JOO)

Octane number of a fuel is defined as the percentage of isooctttne in a mixture of isooctane and n-
heptane, which has the same knocking characteristics as that of the foe! under examination, under
Jt1me set ofconditions. Thus, a fuel with octane number 80 is one which has the same combustion
h cteristics as a 80:20 mixture of isooctane and n-heptane.
tiknocking agents Octane number of gasoline can be increased by addition of additives like
ol and alcohol. This process is called "blending". .
The antiknock properties of gasoline are usually increased by adding tetraethyl lead m!J.
Pb (C,H ) and rhe process is called "do ping". TEL is a colourless liquid with a sweet odour but
- 54 --=...----
ir 1s highly poisonous. About 0.5 ,ml of TEL per litre is added for motor fuels and about 1 ml of
TEL per litre is added for aviation fuel. Gasoline contdining TEL is coloured ,vith 2% red dye to
indicate its poisonous nature.
It is believed that knocking is a free radical mechanism. During combustion Pb(C2H 5\ forms
Pb and PbO. These acr as free radical chain inhibitors and hence the propagation of the chain
reacti on leading to knocking docs not take place.
However lead and lead oxide vapours so form ed contaminate the atmosphere. Lead oxide is
rapidly reduced to metall ic lead which is deposi ted on the spark plug, cylinder walls and piston
head. Hence, it is harmful to rhe engi ne. In order to solve these problems ethylene dibromide
 •v
' L; - L::.ngineeri,
zg
c•foeniirr rp: Fune/an , - L - -
· h l l ia s ,znd Appl101tto1Js
( CH Br) · l
_2 4 . 2 Is a so added, so tha r l ead for d . . '
escapes in to d-ie atn-iosphe r e. n1e is converted into te:>ad brotnide, which is v o latile and

J)

Owing to harmful effects oF lead, these days unleaded petrol is being u sed .
Unleaded Petrol It is one '\Vhere octane number is increased without the addition of lead
compounds. High octane number compounds such as isopentane, isooctane, ethylbenzene,
isopropyl benzene, methyl tertiary butyl ether (MTBE) are used. Out of these, MTBE is preferred
because it con rains oxygen in the form of ether group and supplies oxygen for the combustion of
petrol in internal combustion engines, thereby reducing peroxy compound formation.
Use oE unleaded petrol requires the use of catalytic converter. A catalyt_ic converter contains a
catalyst (rhodium), which convens the toxic gases (CO and NO) to harmless gas~s (CO 2 and N 2 ,
respectively). Moreover, it oxidizes unburnt hydrocarbon into CO2 and H 2 0 .
 ' ' ' ' ' - ' "-" --'---' 1 , ....., 1 .... . ._ ,> t .. • . . - i.,
C - - -
V

Ceta11e Rnti11g!Ceta11e nu.mher Cctanc number is a measure of ignition quality of a diesel fuel. It
is often mistaken as a measure of the fuel qu;ility. It is actually a measure of the fuel 's ignition delay.
It is 1hc measure of the case with which th e fuel will ignite under compression. The hydrocarbon
Cct:rnc (n-hcxadecane) has a very short ignition delay as compared to any diesel fuel and is assigned
an arbfrrary v;ilue of I 00. a -methyl naphthaJene has a long ignition delay compared to any ocher
diesel fuel and hence is assigned a value of O (zero) .

CH 3
CH r (CH 2 ) 1,i -CH3
Cerane
or
n-hexadecane
a- mechylnaphrhalene
(Cetane no. = 100)
(Cetane no =0)

The cetane number ofa dieselfuel is defined as the percentage ofcetane (n-hexadecane) in a mixture of
cetane and a- methylnaphthalene, which will have the same ignition characteristics as the fuel under
test, under the same conditions. For example, a diesel fuel will be assigned a cetane number of 60
if it has the same ignition characteristics as that of a mixture of 60% cetane (n-hexadecane) and
4 0% a-methylnaphthalene. The cetane value of a fuel depends upon the nature and composition
of hydrocarbon. The straight chain hydrocarbons ignite quite readily, although aromatics do
not ignite easily. Ignition quality order among the constituents of diesel engine fuels in order of
decreasing cetane number is as follows:

n-alkanes > naphthalene > alkenes > branched alkanes > aromatics

Thus, hydrocarbons which are poor gasoline fuels are quite good diesel fuels.
The cetane number of a diesel fuel can be raised by addition of small quantity of certain "pre
-ignition dopes" such as ethylnitrite, isoamyl nitrite, acetone peroxide etc.
High-speed and Low speed diesel In a high-speed diesel engine the time lag in getting the diesel
droplets h eated to ignition point is very small, abo_ut 11500th of a second. Such diesel engines
require diesel with cetan e number in excess of 45 (up to 60) . On the other hand, low speed diesel
requires a cetane number of abo ut 25. Cetane number of medium speed diesel is about 35 .

Reforming

Reforming is the process of improving the antiknocking characteristics of gasoline by bringing

about certain structural modifications in it. T h e modifications are due to the rearrangement of
molecules witho u t disturbing their average molecul ar weight. The m ai n reactions involved in
reforming process are
 I·

d Ap,h/ications
50 • Engineering Chemistry: hmdamenta Is an r

(i) Dehydrogenation (removal of hydrogen)

CH 3

0
Cyclohexanc
- JH, ~ @}
Benze nc
6Mechyl
cyclohexane
Toluene

. fi II 0 wed by cyclization)
(ii) Dehydrocycliza.tion (Removal of hydrogen °

Toluene
Methyl
cyclohexane
n-heptane

Hydrocracking (Breaking of the molecule in presence of Hz)

CH 3-(CH 2)8-CH 3 + H2 2CH 3-(CH 2) 3-CH 3

n-pentane
n-decane

lsomeriza.tion

CH 3-(CH)
2 4
- CH 3 ➔ CH 3-CH-CH 2-CH 3
n-hexane I
CH 3
2-methylpentane

Reforming can be carried out either thermally or in the presence of a catalyst.

Thermal Reforming In this process, the straight run gasolines are heated to a temperature of 500
_ 600°C ro a pressure of about 85 kg/cm 2• The degree of reforming is controlled by rapid cooling
(quenching) with an oil spray. The reformed products are fractionated to remove residual gases.
Alkanes and alkenes formed due to cracking may undergo dehydrogenation and cyclization to form
naphthalenes. n-alkanes may also get converted into branched chain hydrocarbons (isomerization) .
Catalytic reforming Catalytic reforming is carried out in the presence of a catalyst (platinum
supported on alumina) . It is carried out at 460 - 530°C and a pressure of 35 -51 kg/cm2. It can be
eith er fixed bed or fluidized bed.