Physical Properties

Baume Gravity (Be)

API Gravity ( API)

The Twadell density for petroleum is always negative as < 1


F 60 at water of lume certain vo a of Mass
F 60 at oil of lume certain vo a of Mass
60
60

=
Density
C 4 at water of lume certain vo a of Mass
C 20 at oil of lume certain vo a of Mass
20
4

=
130
140
60
60
0
=

Be
5 . 131
5 . 141
60
60
0
=

API
Twadell density (T
W
)
) 1 ( 200
60
60
0
=
w
T
60
60

Alkanes Naphthanes Aromatics

C
6
H
14
< C
6
H
12
< C
6
H
6

In the case of pure hydrocarbons with the same number of carbon atoms in the
molecule, the specific gravity increases in the following order

Variation of density specific gravity with chemical composition
2
0 0 4 4
) ( ) (
0
t t b t t a
t t
+ + =
) (
0 4 4
0
t t a
t t
+ =
For small ranges of temperature of 40 - 50
0
C
Variation of specific gravity with temperature
T
0
is the initial temperature
a & b are constants

For Newtonan Fluids
units of = centi poise
From Poiseuilles Law
Q the quantity discharged in unit time
r radius of the tube
l length of the tube
AP pressure difference between the ends of the capillary
q absolute or dynamic viscosity

Viscosity
Absolute or dynamic viscosity
F
V=0
dx
dV
A
F
= q
q
q
t
8
4
P r
Q
A
=
x
A
A
Units of kinematic viscosity that is generally used is centistokes (cst)
) ( Density
) ( viscosity Absolute
) ( viscosity Kinematic

q
v =
Kinematic Viscosity
Arbitrary scales of viscosity

a. Saybolt Seconds Universal (SSU) or Saybolt Universal Seconds (SUS)
b. Redwood Seconds
Redwood No 1 - for less viscous liquids
Redwood No 2 - for more viscous liquids
c. Engler Seconds

t- Saybolt Universal Viscosity in Seconds


E Engler viscosity in seconds

Measurement of viscosity on three scales
Relationship of the arbitrary values of viscosity and the kinematic viscosity
(empirical equations)
t
t
7 . 149
219 . 0 = v
E
E
0
0
0634 . 0
0731 . 0 = v
rod with fixed metal ball
metal cup
measuring cylinder
aperture
thermometer
Water bath

variation is non-linear


as temp viscosity


a linear variation is shown if the quantity log.log (v + 0.8) = W is plotted against log T.



Variation of viscosity with temperature
temp
v
Log T
W
T T
1
T
2
W
2
W
1
W
Viscosity of mixtures
Viscosity of a mixture of known composition
n n r r m
x x x x
3 / 1 3 / 1
2
3 / 1
2 1
3 / 1
1
3 / 1
...... ...... q q q q q + + + + =
q
m
mean viscosity of mixture
q
r
absolute viscosity of component r at the given temperature
x
r
molal fraction of component r
Viscosity of a binary mixture
1
q
2
q
q
1
viscosity of the high viscous oil
q
2
viscosity of the high viscous oil
q required viscosity at the same temperature
x percentage of low viscous oil needed to obtain
the required viscosity q

x
q
% of low viscous oil
Log T
W
B
T
1
M

W
1
A
O

N



Percentage of B needed to obtain the required
viscosity W
1
at temperature T
1
is given by

MN
OM
%B=
Viscosity Index
temp
v
H
L
U
100 F

210 F

100
H L
U L
Index Viscosity

=
L viscosity of L series oil at 100
0
F
H viscosity of H series oil at 100
0
F
U viscosity of unknown oil at 100
0
F
Alternatively,



2 . 721 070 . 12 2160 . 0 L
2
+ + = S S
4 . 475 568 . 12 0408 . 0 H
2
+ + = S S

S - viscosity in Saybolt Universal Seconds at 210
0
F of the unknown oil

Variation of viscosity Index with chemical composition
Paraffin
lowest viscosity, highest VI
Paraffin with a side branch has a lower viscosity and a slightly greater VI than the straight
chain compounds.
Napthenes
has a higher viscosity and lower VI than paraffin.
Introduction of side chains on the ring reduces the viscosity and increases the VI.
Aromatics
highest viscosity, lowest VI
Introduction of side chains on the aromatic ring reduces the viscosity and increases the VI

Viscosity VI
a>n>p a<n<p
Vapour pressure
r
e
rate of escape
r
r
rate of return
at the beginning r
e
>>> r
r

but gradually r
e
~ r
r

when r
e
= r
r
a state of dynamic equilibrium

Variation of vapour pressure with temperature
v
T = t
T = t > t
When temperature is increased, molecular speed in liquid
increses
r
e
>>> r
e

At the dynamic equilibrium r
e
= r
r

Variation of vapour pressure of a liquid with temperature is non-linear

Clausius Clayperon Eq
n
indicates that rate of variation of vapour pressure
with absolute temperature,

i.e. v
g
>>> v
l

v
g
- v
l
~ v
g


P
T
T V V
H
dT
dP
l g
v

A
=
) (
- enthalpy of vaporization
V
g
molar volume of gas
V
l
molar volume of liquid
v
H A
P RT
H
T V
H
dT
dP
v
g
v
/
2
A
=

A
=
2
T
dT
R
H
P
dP
v

A
=
By integrating,
C
T R
H
v
+
A
=
1
lnP
ln P
1/T
P
T
Determination of vapour pressure
Distillation Curve
Distillation curve - a graph of the percent of oil distilled versus the temperature
Initial boiling point - temperature at which the first drop of liquid distills
temperature of zero percent distilled/vaporized
Types
1. The true boiling point curve (TBP curve)
depicts the percent distilled corresponding to various temperatures
under conditions close to fractional distillation
2. The Equilibrium Flash Vaporization Curve (EFV Curve)
gives data of distillation when the distillation is done under conditions
where no fractional distillation takes place
3. The ASTM distillation curve
is obtained using a standard apparatus specified by the American Society
for Testing Materials
has no parallel in industry and is confined to laboratory
could be obtained very easily, nature of other curves could be obtained
TBP Curve
1. heater
2. fractionating column, which is packed with
beads, glass or rings
3. distillation flask
4. valve
5. thermometer
6. receiver or a measuring cylinder to collect
the distilled liquid
7. head of the column
8. Condenser

Standards (differ in the height of the column)
1. US Bureau of Mines, Hempel distillation
unit
2. ASTM D285

Could be graded as (say, 15:5 distillation)
equivalent no of theoretical plates in a
standard column (say, 15)
reflux ratio (say, 5:1)
EFV Curve
1. flask
2. heating coil
3. electrical resistance
4. vaporization chamber
5. thermometer
6. cooler/condenser
7. receiver
8. heat exchanger
9. receiver
10. stirrer
11. lead bath
Coordinate of the plot
temperature of the chamber
amount of liquid separated
amount of condensed
ASTM Curve
1. distillation flask (150
ml capacity)
2. Bunsen burner
3. brass tube
4. water tank
5. measuring cylinder
Similar to Engler distillation
Distillation rate- 5 ml/min adjust by heating the oil and cooling the vapour
TBP EFP ASTM
Every compound
boils at its
proper boiling
point
Fast moving low boiling molecules
exchange their kinetic energy to the
slow moving high boiling particles.
This causes the low boiling
molecules to boil at a higher
temperature, and the high boiling
molecules to boil at a lower
temperature.
A very small amount of
fractionation occurs
along the small length
of the empty tube near
the neck of the flask
Lowest IBP Highest IBP Intermediate
Highest FBP Lowest FBP Intermediate

Comparison of Curves
EFV
TBP
ASTM

The temperature at which the saturated vapor pressure of the liquid
becomes equal to the external pressure
Normal boiling point (NBP)
when the external pressure is one atmosphere
Boiling Point
C
T
B
+
=
188 . 18
18012
1 . 813
NBP (in
0
C) of n-alkanes can be estimated
C- No. of carbon atoms in the paraffin
Average boiling point

a. Temperature corresponding to 50% distilled on the ASTM or TBP(t
50%
)
b. Volumetric average Boiling Point (VABP)


c. Weight Average Boiling Point (WABP)


5
% 90 % 70 % 50 % 30 % 10
t t t t t
VABP
+ + + +
=
r
BP
n
r
r
t w WABP

=
=
1
T
r
r
W
W
w =
where W
r
weight of component r
W
T
Total weight of mixture
T
BPr
Boiling point of component r

d. Molal Average Boiling Point (MABP)
e. Cubic Average Boiling Point (CABP)
f. Mean Average Boiling Point (MeABP)
Burning of Hydrocarbons

a. Calorific value heat of combustion or heating value

Net Calorific Value
Gross Calorific Value
NCV = GCV heat of condensation of water vapour
60
60
8793 50244 = GCV
GCV (in kJ/kg) of petroleum oils is given by,
H GCV NCV 45 . 50 =
When hydrogen content by weight of a fuel, H, is known
60
60
15 26 = H
Heat of combustion of a mixture of hydrocarbon gases




Where, Q
s(r)
- heat of combustion of component r
Y
r
molal fraction of component r
r
n
r
r s m s
Y Q Q =

=1
) ( ) (
Limits of explosion (limits of combustion or limits of inflammability)
5.3 13.9
86.1 94.7
Volume of methane
Volume of air
Effect of pressure on limits of explosion
Increase in pressure has little effect on the lower limit, but tends to increase
the upper limit
Estimation of explosive limits
Lower Upper
Gas or vapour+O
2
1/A-1 4/A
Gas or vapour + air 1/4.85(A-1) 4/4.85-A
A no. of oxygen atoms needed for burning of one molecule of fuel

Self ignition temperature
Two ways to burn a combustible mixture (i.e. a mixture within the limits of explosion).
by introducing a flame match, candle or spark plug
by raising the temperature of the mixture until the self ignition temperature
of the gas is reached.
Definition
The temperature at which ignition takes place in a combustible mixture without
the presence of an external flame
For the same number of carbon atoms, variation of self ignition temperature.
paraffinic < naphthenic and olefinic < aromatic
Iso- paraffins> n-parafins
Some substances like iron sulfide lowers, lead tetra ethyl increases
Flash Point
temperature at which the vapour above a liquid would momentarily flash when a
flame is produced to the surface
Fire point
temperature at which the vapour above a liquid would catch fire and the flame
becomes selfmaintaining
Determination
Cleveland Open Cup Tester
Tag Closed Cup Tester
Pensky Martens Closed Cup Tester
Estimate of flash point of a petroleum fraction using data from the distillation curve
t = 0.64T
m
- 62
where t flash point in
0
C
t
m
mean temperature of the values of 0% and 10% of the ASTM curve in
0
C

Cloud Point
temperature at which a temporary turbidity appears in the oil.
Pour Point
temperature at which the liquid virtually solidifies and does not pour.
These temperatures are important for all petroleum fractions used at low
temperatures/cold climates (as aviation fuel and lubricants)