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The Properties of RP-1 and RP-2
MIPR F1SBAA8022G001
Thomas J. Bruno
Physical and Chemical Properties Division
National Institute of Standards and Technology
Boulder, CO
Approved for public release; distribution unlimited.
Executive Summary:
AFOSR-MIPR F1SBAA8022G001
Characterization of a real fuel: JP-8

i.e., chemical analysis, VLE, , , , Cv
Complete RefProp fluids files for RP-1 and RP-2

Perform thermal decomposition studies on RP-2:
no additives
with THQ, tetralin, +100 package
NIST Staff:
Tom Bruno
Arno Laesecke
Stephanie Outcalt
Richard Perkins
Jason Widegren
Marcia Huber
Eric Lemmon
and Students:
Beverly Smith
Lisa Ott
Kari Brumbeck
Amelia Hadler
Tara Lovestead
First, a bit of history
RP-1:
Rocket Propellant 1 (refined

petroleum 1)
Kerosene base, used with LOX

in rockets such as the Saturn V
Density 0.81 - 1.02 g/mL
Oxidizer to fuel ratio = 2.56
Temperature of combustion =
3,670 K
RP-2
A highly hydrotreated kerosene

Little or no sulfur
Few if any aromatics
Clear at present, no added dye
NASA RP-1 Project

We obtained a sample of RP-1, 2002:
P000016660
Chemical analysis revealed presence of many aromatics and
alkenes
An extensive series of measurements and correlations

was done.
At the December 03 workshop, it was decided that the
lot was unusual.
A follow-on project determined compositional variability.
Our results were summarized

in NISTIR 6646, and the
preliminary RP-1 fluid file was
developed
We start with:
Comprehensive chemical analysis
Distillation curves (of the advanced
variety)
RP-1 Distillation Curves

260.0
Temperature, Tk, C
250.0
Curve is far more typical

of a complex fluid
240.0
RP-1, in spec
RP-1, out of spec
230.0
220.0
210.0
Curve is dominated by a
few major components
200.0
0
10
20
30
40
50
60
70
80
90
100
Volume Fraction, %
280.0
270.0
Temperature, Tk ( C)
260.0
RP-1 and RP-2 are very similar in volatility, while

TS-5 is slightly less volatile
250.0
240.0
230.0
220.0
RP-1
RP-2
TS-5
210.0
200.0
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
Distillate Volume Fraction

Now, complete the property

suite:
, , , Cv, etc.
, kgm-3
860
Compressed Liquid Density of RP-1
Density:
840
820
Experimental details
were discussed earlier
800
780
760
740
720
700
680
660
250 270 290 310 330 350 370 390 410 430 450 470 490
T, K
, kgm-3
860
Compressed Liquid Density of RP-2

840
And for RP-2:

820
800
780
760
740
720
700
680
660
250 270 290 310 330 350 370 390 410 430 450 470 490
T, K
w / ms-1
1400
RP-1
Speed of sound of RP-1 and

RP-2 as a function of
temperature at ambient
pressure.
RP-2
1350
1300
1250
1200
1150
1100
270
280
290
300
310
320
330
340
350
T/K
s / TPa-1
1050
Adiabatic compressibility
data of RP-1 and RP-2 as
a function of temperature
at ambient pressure.
1000
950
900
850
800
750
700
RP-1
650
RP-2
600
270
280
290
300
310
320
330
340
350
T/K
/ mm2s-1
2.4
Kinematic viscosity of RP-1

and RP-2 as a function of
temperature at ambient
pressure.
2.2
1.8
1.6
1.4
RP-1
1.2
RP-2
0.8
0.6
280
290
300
310
320
330
340
350
360
370
380
T/K
Thermal Conductivity of RP-1 (New Sample)

0.130
0.120
. -1 -1
/ Wm K
0.110
0.100
300 K
350 K
400 K
450 K
500 K
550 K
0.090
0.080
0.070
0
10
20
30
40
50
60
70
P / MPa
Thermal Conductivity of RP-2

0.130
0.120
. -1 -1
/ Wm K
0.110
0.100
300 K
350 K
400 K
450 K
500 K
550 K
0.090
0.080
0.070
0
10
20
30
40
50
60
70
P / MPa
In parallel, a study of decomposition

was done:
Decomposition studies have been part of
the NIST protocol since we left cryogenics
With RP-2, the decomposition is important
as a measurement.
straight RP-2, RP-2 with additives, corrosivity
studies
Explicit consideration of sample

decomposition was begun of
necessity:
Straty, G.C., Palavra, A.M.F., Bruno, T.J., PVT Properties of

Methanol at Temperatures to 300 oC, Int. J. Thermophys, 7(5), 1077,
1986.
Straty, G.C., Ball, M.J., Bruno, T.J., PVT of toluene at temperatures

to 673 K, J. Chem. Eng. Data, 33,115,1988.
Experimental effort involves numerous high

value, one-of-a kind apparatus:
VLE Instruments
Viscometers
torsional crystal
Stabinger
gravitational
Densimeters
dual sinker
rapid screening
Thermal Conductivity
low and high temperature hot wire
Speed of Sound
Etc.
At only 100 oC, the

sample decomposed into
CO, H2, and synthetic
products
Samples are thermally stressed in stainless

steel ampoule reactors
ampoule reactor
thermostat
insulated box
slots for reactors
stainless steel
block (one of two)
temperature
probe
heaters
PID temperature
controller
Ampoule reactors:
Temperatures to 450 oC
Pressures to 10,000 psi
(once, by accident, to 36,000 psi)
Extent of decomposition determined by

analysis
GC-FID of RP-2
Unheated sample
After 10 min at 450 C
The light
decomposition
products are
used for the
kinetic analysis
Emergent suite of decomposition products
Pseudo-first-order kinetics on the emergent

suite of decomposition products
A
d [ A] d [ B]
=
= k [ A]
dt
dt
t1/ 2
The assumption of
first-order kinetics
is a necessary
approximation for
these complex
mixtures.
ln 2
=
k
Separate phase analysis is performed

determine thermal or catalytic mechanisms
Gas-liquid
separation
device
Liquid and gas phases analyzed by FTIR, GC-FID and GC-MS

Bruno, T.J., Conditioning of multiphase flowing samples for chemical analysis, Sep.
Sci. Tech., 40, 1721-1732, 2005.
Decomposition kinetics of RP-2

75
75
400 C
Product Suite Area
Product Suite Area
375 C
50
25
500
1000
Reaction Time / min
1500
50
25
50
100
150
200
250
Reaction Time / min
The rate constant for decomposition, k', is obtained from the fit.

200
160
450 C
Product Suite Area
Product Suite Area
425 C
120
80
40
50
100
Reaction Time / min
150
150
100
50
10
20
30
40
50
Reaction Time / min
The rate constant for decomposition, k', is obtained from the fit.

200
Product Suite Area
450 C
150
425 C
100
375 C
400 C
50
500
1000
Reaction Time / min
1500
Rate constants for RP-2 decomposition

375
400
425
450
(k 1) / s
5
(1.33 0.30)10
5
(9.28 2.01)10
4
(1.33 0.33)10
4
(5.47 0.80)10
-7
-8
ln k'
T / C
-9
-10
-11
-12
1.35
1.40
1.45
1000/T
1.50
1.55

200
Product Suite Area
RP-1 at 450 C
150
100
50
10
20
30
Reaction Time / min
40
50
The decomposition of RP-1 and RP-2 is very similar.

Andersen, P.C., Bruno, T.J., Thermal decomposition of RP-1 rocket propellant, Ind. Eng.
Chem. Res., 44, 1670-1676, 2005.
Comparison of RP-1 and RP-2 decomposition

200
Product Suite Area
450 C
150
100
50
RP-2
RP-1
10
20
30
40
Reaction Time / min
Comparison of Jet A with RP-1

and RP-2
-6
ln k'
-8
-10
RP-1
R P -1
RP-2
R P -2
Jet
J e At A
-12
1.35
1.40
1.45
1.50
1.55
1000 / T
Comparison of RP-1 and RP-2 decomposition

RP-1
1
T / C
(k 1) / s
5
(1.13
0.04)10
375
4
400 (1.19 0.33)10
4
425 (3.08 0.77)10
4
(5.84
1.33)10
450
RP-2
1
(k 1) / s
(1.33 0.30)105
(9.28 2.01)105
(1.33 0.33)104
(5.47 0.80)104
Decomposition of RP-2 with additives

RP-2 with 5% tetralin
RP-2 with 5% THQ

N
H
RP-2 with 256 ppm of the additive mixture in JP-8 +100

- contains a chelator, antioxidant, and surfactant
Hydrogen donors increase thermal stability by interrupting

radical decomposition pathways.
Product Suite Area
80
60
RP-2
RP-2 + 100 additive
RP-2 + 5% tetralin
RP-2 + 5% THQ
375 C
5% THQ lowers
the rate of
decomposition
by about an
order of
magnitude.
40
20
400
800
1200
Reaction Time / min
1600
Product Suite Area
160
120
RP-2
RP-2 + 100 additive
RP-2 + 5% tetralin
RP-2 + 5% THQ
425 C
The stabilizing
effect is smaller
at higher
temperature.
80
40
30
60
90
Reaction Time / min
120
Concentration of THQ during decomposition

375 C
3
2
3
2
0
0
400
800
T im e / m in
425 C
M ass % THQ
M ass % THQ
1200
1600
50
100
150
200
250
T im e / m in
Parallels results with B100 (biodiesel):

430.0
B100 + 1% t -decalin
B100 + 1% tetralin
420.0
420.0
410.0
410.0
410.0
390.0
380.0
370.0
400.0
400.0
420.0
430.0
430.0
B100 + 1% THQ
390.0
380.0
370.0
400.0
390.0
380.0
370.0
360.0
360.0
360.0
350.0
350.0
350.0
340.0
340.0
0.0
0.2
0.4
0.6
0.8
1.0
340.0
0.0
0.2
0.4
0.6
0.8
1.0
0.0
0.2
0.4
0.6
0.8
1.0
Lower is better!
A clear high-temperature stabilization effect occurs.
Stabilization of RP-2:
>>
tetrahydroquinoline
>>>>
tetralin
+100
Stabilization of B100:
>
tetrahydroquinoline
>>
t-decalin
tetralin
Corrosivity of decomposed RP-1
An improved copper strip corrosion test, developed at

NIST, was used to determine the corrosivity of four
liquids based on RP-1:
(1) RP-1
(2) RP-1 + 0.14 % allyl sulfide
(3) RP-1 after 2 h at 400 C
(4) RP-1 + 0.14 % allyl sulfide after 2 h at 400 C
ETP copper
coupons
1018 steel
coupons
RP-1 + 0.14 % allyl sulfide
Decomposed RP-1
Decomposed
RP-1
RP-1 + 0.14 % allyl sulfide, decomposed
RP-1, decomposed
GC analysis with a flame ionization detector
RP-1
Decomposition greatly increased the corrosivity of the mixture,

and slightly increased the corrosivity of RP-1.

Sample
CSCT
L*
[sulfur] / ppm
RP-1 + 0.14 % allyl sulfide, decomposed
4a
160
3.1
1a
199
28.8
RP-1, decomposed
1b
189
not detected
RP-1
untarnished
197
not detected
Rocket and Hypersonic Vehicle

Propellant Workshop:
Place:
NIST Boulder Laboratories
Time:
Sept. 25 - 26, 2008
Rollout of RP fluid files
Acknowledgements:
AFRL-EAFB
Matt Billingsley, Ron Bates and Steve
Hanna
Tim Edwards, AFRL-WPAFB
Product Suite Area
160
120
RP-2
RP-2 + 100 additive
RP-2 + 5% decalin
RP-2 + 5% tetralin
RP-2 + 5% THQ
425 C
80
40
30
60
90
Reaction Time / min
120
Thermal Conductivity of RP-1 (2003)

0.130
0.120
-1 -1
/Wm K
0.110
300
350
400
450
500
547
608
650
K
K
K
K
K
K
K
K
0.100
0.090
0.080
0.070
0.45
0.50
0.55
0.60
0.65
0.70
0.75
0.80
0.85
/ g cm-3

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The Properties of RP-1 and RP-2

Approved for public release; distribution unlimited.

Characterization of a real fuel: JP-8

Complete RefProp fluids files for RP-1 and RP-2

Approved for public release; distribution unlimited.

Approved for public release; distribution unlimited.

First, a bit of history

Approved for public release; distribution unlimited.

Rocket Propellant 1 (refined

Kerosene base, used with LOX

Density 0.81 - 1.02 g/mL

Oxidizer to fuel ratio = 2.56

Approved for public release; distribution unlimited.

A highly hydrotreated kerosene

Approved for public release; distribution unlimited.

NASA RP-1 Project

An extensive series of measurements and correlations

Our results were summarized

Approved for public release; distribution unlimited.

Approved for public release; distribution unlimited.

RP-1 Distillation Curves

Curve is far more typical

RP-1 and RP-2 are very similar in volatility, while

Distillate Volume Fraction

Now, complete the property

Approved for public release; distribution unlimited.

Compressed Liquid Density of RP-1

Compressed Liquid Density of RP-2

And for RP-2:

Speed of sound of RP-1 and

Kinematic viscosity of RP-1

Approved for public release; distribution unlimited.

Thermal Conductivity of RP-1 (New Sample)

Thermal Conductivity of RP-2

In parallel, a study of decomposition

Approved for public release; distribution unlimited.

Explicit consideration of sample

Straty, G.C., Palavra, A.M.F., Bruno, T.J., PVT Properties of

Straty, G.C., Ball, M.J., Bruno, T.J., PVT of toluene at temperatures

Approved for public release; distribution unlimited.

Experimental effort involves numerous high

At only 100 oC, the

Approved for public release; distribution unlimited.

Samples are thermally stressed in stainless

Approved for public release; distribution unlimited.

Approved for public release; distribution unlimited.

Approved for public release; distribution unlimited.

Extent of decomposition determined by

After 10 min at 450 C

Emergent suite of decomposition products

Approved for public release; distribution unlimited.

Pseudo-first-order kinetics on the emergent

Approved for public release; distribution unlimited.

Separate phase analysis is performed

Liquid and gas phases analyzed by FTIR, GC-FID and GC-MS

Decomposition kinetics of RP-2

Product Suite Area

Reaction Time / min

Reaction Time / min

Approved for public release; distribution unlimited.

Decomposition kinetics of RP-2

Product Suite Area