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Approved for public release; distribution unlimited. 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
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Page 1: The Properties of RP-1 and RP-2 MIPR F1SBAA8022G001 for public release; distribution unlimited. The Properties of RP-1 and RP-2 MIPR F1SBAA8022G001. Thomas J. Bruno. Physical and Chemical

Approved for public release; distribution unlimited.

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

Page 2: The Properties of RP-1 and RP-2 MIPR F1SBAA8022G001 for public release; distribution unlimited. The Properties of RP-1 and RP-2 MIPR F1SBAA8022G001. Thomas J. Bruno. Physical and Chemical

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Executive Summary: AFOSR-MIPR F1SBAA8022G001

Characterization of a real fuel: JP-8–

i.e., chemical analysis, VLE, ρ, υ, λ, 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

Page 3: The Properties of RP-1 and RP-2 MIPR F1SBAA8022G001 for public release; distribution unlimited. The Properties of RP-1 and RP-2 MIPR F1SBAA8022G001. Thomas J. Bruno. Physical and Chemical

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NIST Staff:

Tom Bruno•

Arno Laesecke

Stephanie Outcalt•

Richard Perkins

Jason Widegren•

Marcia Huber

Eric Lemmon

Page 4: The Properties of RP-1 and RP-2 MIPR F1SBAA8022G001 for public release; distribution unlimited. The Properties of RP-1 and RP-2 MIPR F1SBAA8022G001. Thomas J. Bruno. Physical and Chemical

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and Students:

Beverly Smith•

Lisa Ott

Kari Brumbeck•

Amelia Hadler

Tara Lovestead

Page 5: The Properties of RP-1 and RP-2 MIPR F1SBAA8022G001 for public release; distribution unlimited. The Properties of RP-1 and RP-2 MIPR F1SBAA8022G001. Thomas J. Bruno. Physical and Chemical

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First, a bit of history

Page 6: The Properties of RP-1 and RP-2 MIPR F1SBAA8022G001 for public release; distribution unlimited. The Properties of RP-1 and RP-2 MIPR F1SBAA8022G001. Thomas J. Bruno. Physical and Chemical

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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

Page 7: The Properties of RP-1 and RP-2 MIPR F1SBAA8022G001 for public release; distribution unlimited. The Properties of RP-1 and RP-2 MIPR F1SBAA8022G001. Thomas J. Bruno. Physical and Chemical

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RP-2

A highly hydrotreated kerosene•

Little or no sulfur

Few if any aromatics•

Clear at present, no added dye

Page 8: The Properties of RP-1 and RP-2 MIPR F1SBAA8022G001 for public release; distribution unlimited. The Properties of RP-1 and RP-2 MIPR F1SBAA8022G001. Thomas J. Bruno. Physical and Chemical

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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.

Page 9: The Properties of RP-1 and RP-2 MIPR F1SBAA8022G001 for public release; distribution unlimited. The Properties of RP-1 and RP-2 MIPR F1SBAA8022G001. Thomas J. Bruno. Physical and Chemical

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Our results were summarized in NISTIR 6646, and the preliminary RP-1 fluid file was developed

Page 10: The Properties of RP-1 and RP-2 MIPR F1SBAA8022G001 for public release; distribution unlimited. The Properties of RP-1 and RP-2 MIPR F1SBAA8022G001. Thomas J. Bruno. Physical and Chemical

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We start with:

Comprehensive chemical analysis•

Distillation curves (of the advanced variety)

Page 11: The Properties of RP-1 and RP-2 MIPR F1SBAA8022G001 for public release; distribution unlimited. The Properties of RP-1 and RP-2 MIPR F1SBAA8022G001. Thomas J. Bruno. Physical and Chemical

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RP-1 Distillation Curves

200.0

210.0

220.0

230.0

240.0

250.0

260.0

0 10 20 30 40 50 60 70 80 90 100

Volume Fraction, %

Tem

pera

ture

, Tk,

C

RP-1, in spec

RP-1, out of spec

Curve is dominated by a few major components

Curve is far more typical of a complex fluid

Page 12: The Properties of RP-1 and RP-2 MIPR F1SBAA8022G001 for public release; distribution unlimited. The Properties of RP-1 and RP-2 MIPR F1SBAA8022G001. Thomas J. Bruno. Physical and Chemical

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200.0

210.0

220.0

230.0

240.0

250.0

260.0

270.0

280.0

0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1

Distillate Volume Fraction

Tem

pera

ture

, Tk (

o C)

RP-1RP-2TS-5

RP-1 and RP-2 are very similar in volatility, while TS-5 is slightly less volatile

Page 13: The Properties of RP-1 and RP-2 MIPR F1SBAA8022G001 for public release; distribution unlimited. The Properties of RP-1 and RP-2 MIPR F1SBAA8022G001. Thomas J. Bruno. Physical and Chemical

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Now, complete the property suite:

ρ, υ, λ, Cv, etc.

Page 14: The Properties of RP-1 and RP-2 MIPR F1SBAA8022G001 for public release; distribution unlimited. The Properties of RP-1 and RP-2 MIPR F1SBAA8022G001. Thomas J. Bruno. Physical and Chemical

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660

680

700

720

740

760

780

800

820

840

860

250 270 290 310 330 350 370 390 410 430 450 470 490

T , K

ρ, kg·m-3

Compressed Liquid Density of RP-1

Density:

Experimental details were discussed earlier

Page 15: The Properties of RP-1 and RP-2 MIPR F1SBAA8022G001 for public release; distribution unlimited. The Properties of RP-1 and RP-2 MIPR F1SBAA8022G001. Thomas J. Bruno. Physical and Chemical

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660

680

700

720

740

760

780

800

820

840

860

250 270 290 310 330 350 370 390 410 430 450 470 490

T , K

ρ , kg·m-3

Compressed Liquid Density of RP-2

And for RP-2:

Page 16: The Properties of RP-1 and RP-2 MIPR F1SBAA8022G001 for public release; distribution unlimited. The Properties of RP-1 and RP-2 MIPR F1SBAA8022G001. Thomas J. Bruno. Physical and Chemical

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1100

1150

1200

1250

1300

1350

1400

270 280 290 300 310 320 330 340 350

RP-1

RP-2

w / m·s-1

T / K

Speed of sound of RP-1 and RP-2 as a function of temperature at ambient pressure.

Page 17: The Properties of RP-1 and RP-2 MIPR F1SBAA8022G001 for public release; distribution unlimited. The Properties of RP-1 and RP-2 MIPR F1SBAA8022G001. Thomas J. Bruno. Physical and Chemical

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600

650

700

750

800

850

900

950

1000

1050

270 280 290 300 310 320 330 340 350

RP-1

RP-2

T / K

κs / TPa-1

Adiabatic compressibility data of RP-1 and RP-2 as a function of temperature at ambient pressure.

Page 18: The Properties of RP-1 and RP-2 MIPR F1SBAA8022G001 for public release; distribution unlimited. The Properties of RP-1 and RP-2 MIPR F1SBAA8022G001. Thomas J. Bruno. Physical and Chemical

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0.6

0.8

1

1.2

1.4

1.6

1.8

2

2.2

2.4

280 290 300 310 320 330 340 350 360 370 380

RP-1

RP-2

ν / mm2·s-1

T / K

Kinematic viscosity of RP-1 and RP-2 as a function of temperature at ambient pressure.

Page 19: The Properties of RP-1 and RP-2 MIPR F1SBAA8022G001 for public release; distribution unlimited. The Properties of RP-1 and RP-2 MIPR F1SBAA8022G001. Thomas J. Bruno. Physical and Chemical

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Thermal Conductivity of RP-1 (New Sample)

0.070

0.080

0.090

0.100

0.110

0.120

0.130

0 10 20 30 40 50 60 70

P / MPa

λ /

W. m

-1K

-1

300 K350 K400 K450 K500 K550 K

Page 20: The Properties of RP-1 and RP-2 MIPR F1SBAA8022G001 for public release; distribution unlimited. The Properties of RP-1 and RP-2 MIPR F1SBAA8022G001. Thomas J. Bruno. Physical and Chemical

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Thermal Conductivity of RP-2

0.070

0.080

0.090

0.100

0.110

0.120

0.130

0 10 20 30 40 50 60 70

P / MPa

λ /

W. m

-1K

-1

300 K350 K400 K450 K500 K550 K

Page 21: The Properties of RP-1 and RP-2 MIPR F1SBAA8022G001 for public release; distribution unlimited. The Properties of RP-1 and RP-2 MIPR F1SBAA8022G001. Thomas J. Bruno. Physical and Chemical

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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

Page 22: The Properties of RP-1 and RP-2 MIPR F1SBAA8022G001 for public release; distribution unlimited. The Properties of RP-1 and RP-2 MIPR F1SBAA8022G001. Thomas J. Bruno. Physical and Chemical

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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.

Page 23: The Properties of RP-1 and RP-2 MIPR F1SBAA8022G001 for public release; distribution unlimited. The Properties of RP-1 and RP-2 MIPR F1SBAA8022G001. Thomas J. Bruno. Physical and Chemical

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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.

Page 24: The Properties of RP-1 and RP-2 MIPR F1SBAA8022G001 for public release; distribution unlimited. The Properties of RP-1 and RP-2 MIPR F1SBAA8022G001. Thomas J. Bruno. Physical and Chemical

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At only 100 oC, the sample decomposed into CO, H2

, and synthetic products

Page 25: The Properties of RP-1 and RP-2 MIPR F1SBAA8022G001 for public release; distribution unlimited. The Properties of RP-1 and RP-2 MIPR F1SBAA8022G001. Thomas J. Bruno. Physical and Chemical

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Samples are thermally stressed in stainless steel ampoule reactors

PID temperature controller

insulated box

heaters

temperature probe

stainless steel block (one of two)

slots for reactors

ampoule reactor thermostat

Page 26: The Properties of RP-1 and RP-2 MIPR F1SBAA8022G001 for public release; distribution unlimited. The Properties of RP-1 and RP-2 MIPR F1SBAA8022G001. Thomas J. Bruno. Physical and Chemical

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Ampoule reactors:

6”

Temperatures to 450 oC

Pressures to 10,000 psi

(once, by accident, to 36,000 psi)

Page 27: The Properties of RP-1 and RP-2 MIPR F1SBAA8022G001 for public release; distribution unlimited. The Properties of RP-1 and RP-2 MIPR F1SBAA8022G001. Thomas J. Bruno. Physical and Chemical

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Page 28: The Properties of RP-1 and RP-2 MIPR F1SBAA8022G001 for public release; distribution unlimited. The Properties of RP-1 and RP-2 MIPR F1SBAA8022G001. Thomas J. Bruno. Physical and Chemical

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Extent of decomposition determined by analysis

The light decomposition products are used for the

kinetic analysis

GC-FID of RP-2

Unheated sample

Emergent suite of decomposition products

After 10 min at 450 °C

Page 29: The Properties of RP-1 and RP-2 MIPR F1SBAA8022G001 for public release; distribution unlimited. The Properties of RP-1 and RP-2 MIPR F1SBAA8022G001. Thomas J. Bruno. Physical and Chemical

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Pseudo-first-order kinetics on the emergent suite of decomposition products

A Bk′

][][][ AkdtBd

dtAd ′==−

kt

′=

2ln2/1

The assumption of first-order kinetics

is a necessary approximation for

these complex mixtures.

Page 30: The Properties of RP-1 and RP-2 MIPR F1SBAA8022G001 for public release; distribution unlimited. The Properties of RP-1 and RP-2 MIPR F1SBAA8022G001. Thomas J. Bruno. Physical and Chemical

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Separate phase analysis is performed determine thermal or catalytic mechanisms

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

Gas-liquid separation

device

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

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Decomposition kinetics of RP-2

The rate constant for decomposition, k', is obtained from the fit.

50 100 150 200 250

75

50

25

Reaction Time / min

Prod

uct S

uite

Are

a

400 °C

500 1000 1500

75

50

25

Reaction Time / min

Prod

uct S

uite

Are

a

375 °C

Page 32: The Properties of RP-1 and RP-2 MIPR F1SBAA8022G001 for public release; distribution unlimited. The Properties of RP-1 and RP-2 MIPR F1SBAA8022G001. Thomas J. Bruno. Physical and Chemical

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Decomposition kinetics of RP-2

The rate constant for decomposition, k', is obtained from the fit.

10 20 30 40 50

Reaction Time / min

200

150

100

50

Prod

uct S

uite

Are

a

450 °C

50 100 150

Reaction Time / min

160

120

80

40

Prod

uct S

uite

Are

a

425 °C

Page 33: The Properties of RP-1 and RP-2 MIPR F1SBAA8022G001 for public release; distribution unlimited. The Properties of RP-1 and RP-2 MIPR F1SBAA8022G001. Thomas J. Bruno. Physical and Chemical

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Decomposition kinetics of RP-2

500 1000 1500Reaction Time / min

Prod

uct S

uite

Are

a

200

150

100

50

450 °C

375 °C400 °C

425 °C

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Rate constants for RP-2 decomposition

T / °C (k ′ ± 1σ) / s−1

375 (1.33 ± 0.30)×10−5

400 (9.28 ± 2.01)×10−5

425 (1.33 ± 0.33)×10−4

450 (5.47 ± 0.80)×10−4

1000/T

ln k

'

1.35 1.40 1.45 1.50 1.55

-11

-10

-9

-8

-7

-12

Page 35: The Properties of RP-1 and RP-2 MIPR F1SBAA8022G001 for public release; distribution unlimited. The Properties of RP-1 and RP-2 MIPR F1SBAA8022G001. Thomas J. Bruno. Physical and Chemical

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Decomposition kinetics of RP-1

The decomposition of RP-1 and RP-2 is very similar.

Reaction Time / min

Prod

uct S

uite

Are

a

10 20 30 40 50

50

100

150

200RP-1 at 450 °C

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

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Comparison of RP-1 and RP-2 decomposition

Prod

uct S

uite

Are

a

200

150

100

50•

RP-2•

RP-1

10 20 30 40Reaction Time / min

450 °C

Page 37: The Properties of RP-1 and RP-2 MIPR F1SBAA8022G001 for public release; distribution unlimited. The Properties of RP-1 and RP-2 MIPR F1SBAA8022G001. Thomas J. Bruno. Physical and Chemical

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Comparison of Jet A with RP-1 and RP-2

R P - 1R P - 2J e t A

1.35 1.40 1.45 1.50 1.55

1000 / T

-6

-8

-10

-12

ln k

'

RP-1RP-2Jet A

Page 38: The Properties of RP-1 and RP-2 MIPR F1SBAA8022G001 for public release; distribution unlimited. The Properties of RP-1 and RP-2 MIPR F1SBAA8022G001. Thomas J. Bruno. Physical and Chemical

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Comparison of RP-1 and RP-2 decomposition

RP-1 RP-2T / °C (k ′ ± 1σ) / s−1 (k ′ ± 1σ) / s−1

375 (1.13 ± 0.04)×10−5 (1.33 ± 0.30)×10−5

400 (1.19 ± 0.33)×10−4 (9.28 ± 2.01)×10−5

425 (3.08 ± 0.77)×10−4 (1.33 ± 0.33)×10−4

450 (5.84 ± 1.33)×10−4 (5.47 ± 0.80)×10−4

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Decomposition of RP-2 with additives

Hydrogen donors increase thermal stability by interrupting radical decomposition pathways.

RP-2 with 5% tetralin

RP-2 with 5% THQ

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

-

contains a chelator, antioxidant, and surfactant

NH

Page 40: The Properties of RP-1 and RP-2 MIPR F1SBAA8022G001 for public release; distribution unlimited. The Properties of RP-1 and RP-2 MIPR F1SBAA8022G001. Thomas J. Bruno. Physical and Chemical

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Decomposition of RP-2 with additives

400 800 1200 1600Reaction Time / min

Prod

uct S

uite

Are

a80

60

40

20

375 °C•

RP-2•

RP-2 + 100 additive•

RP-2 + 5% tetralin•

RP-2 + 5% THQ5% THQ lowers

the rate of decomposition

by about an order of

magnitude.

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Decomposition of RP-2 with additives

30 60 90 120Reaction Time / min

Prod

uct S

uite

Are

a

160

120

80

40

425 °C•

RP-2•

RP-2 + 100 additive•

RP-2 + 5% tetralin•

RP-2 + 5% THQThe stabilizing

effect is smaller at higher

temperature.

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Concentration of THQ during decomposition

0

1

2

3

4

5

6

0 5 0 1 0 0 1 5 0 2 0 0 2 5 0T im e / m in

Mas

s%

THQ

0

1

2

3

4

5

6

0 4 0 0 8 0 0 1 2 0 0 1 6 0 0

T im e / m in

Mas

s%

THQ

375 °C 425 °C

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B100 + 1% THQ

340.0

350.0

360.0

370.0

380.0

390.0

400.0

410.0

420.0

430.0

0.0 0.2 0.4 0.6 0.8 1.0

Distillate Volume Fraction

Tem

pera

ture

, Tk (

o C)

B100 + 1% tetralin

340.0

350.0

360.0

370.0

380.0

390.0

400.0

410.0

420.0

430.0

0.0 0.2 0.4 0.6 0.8 1.0

Distillate Volume Fraction

Tem

pera

ture

, Tk (

o C)

Parallels results with B100 (biodiesel):B100 + 1% t -decalin

340.0

350.0

360.0

370.0

380.0

390.0

400.0

410.0

420.0

430.0

0.0 0.2 0.4 0.6 0.8 1.0

Distillate Volume Fraction

Tem

pera

ture

, Tk (

o C)

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Lower is better!

A clear high-temperature stabilization effect occurs.

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tetrahydroquinoline t-decalin tetralin

> ≈ >>

Stabilization of B100:

Stabilization of RP-2:

>>

tetrahydroquinoline tetralin +100

>>>>

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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

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ETP copper coupons

1018 steel coupons

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Corrosivity of decomposed RP-1

RP

-1, d

ecom

pose

d

RP-1 + 0.14 % allyl sulfide, decomposed

RP-1

RP

-1 + 0.14 % allyl sulfide

Decomposition greatly increased the corrosivity of the mixture, and slightly increased the corrosivity of RP-1.

Decomposed RP-1

RP-1 + 0.14 % allyl sulfide

DecomposedRP-1 + 0.14 % allyl sulfide

RP-1

GC analysis with a flame ionization detector

Decomposed RP-1

RP-1 + 0.14 % allyl sulfide

DecomposedRP-1 + 0.14 % allyl sulfide

RP-1

GC analysis with a flame ionization detector

Decomposed RP-1

RP-1 + 0.14 % allyl sulfide

DecomposedRP-1 + 0.14 % allyl sulfide

RP-1

GC analysis with a flame ionization detector

Decomposed RP-1

RP-1 + 0.14 % allyl sulfide

DecomposedRP-1 + 0.14 % allyl sulfide

RP-1

GC analysis with a flame ionization detector

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Corrosivity of decomposed RP-1

Sample CSCT L* [sulfur] / ppmRP-1 + 0.14 % allyl sulfide, decomposed 4a 160 3.1

RP-1 + 0.14 % allyl sulfide 1a 199 28.8RP-1, decomposed 1b 189 not detected

RP-1 untarnished 197 not detected

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Rocket and Hypersonic Vehicle Propellant Workshop:

Place:NIST Boulder Laboratories

Time:Sept. 25 -

26, 2008

Rollout of RP fluid files”

Page 51: The Properties of RP-1 and RP-2 MIPR F1SBAA8022G001 for public release; distribution unlimited. The Properties of RP-1 and RP-2 MIPR F1SBAA8022G001. Thomas J. Bruno. Physical and Chemical

Approved for public release; distribution unlimited.

Acknowledgements:

AFRL-EAFB

Matt Billingsley, Ron Bates and Steve Hanna

Tim Edwards, AFRL-WPAFB

Page 52: The Properties of RP-1 and RP-2 MIPR F1SBAA8022G001 for public release; distribution unlimited. The Properties of RP-1 and RP-2 MIPR F1SBAA8022G001. Thomas J. Bruno. Physical and Chemical

Approved for public release; distribution unlimited.

Decomposition of RP-2 with additives

30 60 90 120Reaction Time / min

Prod

uct S

uite

Are

a

160

120

80

40

425 °C•

RP-2•

RP-2 + 100 additive•

RP-2 + 5% decalin•

RP-2 + 5% tetralin•

RP-2 + 5% THQ

Page 53: The Properties of RP-1 and RP-2 MIPR F1SBAA8022G001 for public release; distribution unlimited. The Properties of RP-1 and RP-2 MIPR F1SBAA8022G001. Thomas J. Bruno. Physical and Chemical

Approved for public release; distribution unlimited.

Thermal Conductivity of RP-1 (2003)

0.070

0.080

0.090

0.100

0.110

0.120

0.130

0.45 0.50 0.55 0.60 0.65 0.70 0.75 0.80 0.85

ρ / g cm-3

λ /

W m

-1K

-1

300 K350 K400 K450 K500 K547 K608 K650 K


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