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Gas chromatographic determination method of automotive petrols parameters (excerpts from MVI.MN 998-99)

1. Designation and application field

This document describes quantitative chemical analysis method of lead-free automotive petrols and its following parameters:

volume, mass and molar part for individual hydrocarbons and groups of normal paraffins, iso-paraffins, aromatics, naphtenes, olefins and oxygenates in range of mass concentration from 0.01 % to 90 %.

fractional part, represented by temperatures of: start of boiling. 10 %. 50 %. 90 % distillation and end of boiling, in the range from 25 to 260°C.

saturated vapour pressure at 37.8°C in range from 20.0 to 100.0 kPa.

motor octane number in range from 70 to 90 units.

research octane number in range from 80 to 100 units.

density at 20°C in range from 700 to 800 g/l.

2. Measurement errors norm

2.1. Method provides determination of volume, mass and molar part of individual hydrocarbons and groups with relative error less than ± 3.6 %. Precision factor is not over 0.7 % relative.

2.2. Method provides parameters determination with errors not over values shown in Table 1.

Table 1. Measurement errors norm for fractional part, saturated vapour pressure, research and motor octane numbers and density determination.

Parameter

Precision

Cross laboratory reproducibility

Accuracy

Range of main abs. errors at confidence probability of 0.95

Fractional part:

       

Start of boiling temperature, °C

   

4.6

± 9.2

Temperature of 10 %, 50 % and 90 % distillation, °C

0.4

0.7

2.0

± 4.1

End of boiling temperature, °C

   

3.2

± 6.5

Saturation vapour pressure P, kPa

1.0

0.030 · P - 0.5

0.057 · P + 2.8

± (0.116·P+5.5)

Motor octane number

0.1

0.2

1.2

± 2.4

Research octane number

0.1

0.2

1.0

± 2.0

Density, g/l

1.2

2.0

1.0

± 4.5

3. Instrumentation, auxiliary devices, materials, reagents

Carrying measurements using that method use the following instrumentation, devices, stuffs and reagents:

3.1. Instrumentation

Gas chromatograph «Tswett-500» on TO 5E1.550.168-01 with flame ionisation detector and capillary inlet.

Micro syringe MSh-10 on TU 5E2.833.106 volume of 10 mkl with scale division value of 0.2 mkl.

Datasystem for collecting. storage and processing of spectrometric information UniChrom-97 on TU RB 14597800.001-98 with relative peak area measurement error not over 1 %.

3.2. Devices

Chromatographic capillary column HP-1 No 19091Z-115 (USA) quartz, with non-polar stationary liquid polydimethylsiloxane phase, length 50 m, diameter 0.32 mm and film thickness of 0.52 mkm.

3.3. Materials

Helium - purity 99.99 % on TU 51-940-80.

Hydrogen - purity 99.99 % on TU 3022-80.

Air - technical on GOST 17433-80.

Appendix

Petrol Analysis Report No 18

File: C:\Unichrom\DB - Petroleum Products\Column HP-1 19091Z-115\Customer petrol.$$$

Method: Customer petrol ( date: 21.10.98. TIME: 15:43 )

Chromatogram: AZS-IV city of Minsk: producer - Novopolotsk Oil Refinery RON 82.0 MON 77.0

Individual components (processed 322 peaks)

No

Name

t'

I lin

I log

vol%

mass%

mol%

g/l

mol/l

1

Ethane

0.05 200.00 200.00 0.023 0.017 0.054 0.130 0.004
2

Propane

0.16 300.00 300.00 0.340 0.266 0.562 1.969 0.045
3

2-methylpropane

0.32 354.19 366.44 0.776 0.584 0.937 4.325 0.074
4

1-butene

0.41 385.20 390.40 0.020 0.016 0.027 0.118 0.002
5

n-butane

0.46 400.00 400.00 3.297 2.599 4.173 19.265 0.331
6

trans-2-buten

0.51 406.52 410.60 0.012 0.010 0.017 0.075 0.001
7

2,2-dimethilpropane

0.53 409.19 414.63 0.024 0.020 0.025 0.146 0.002
8

cis-2-buten

0.59 416.56 425.01 0.013 0.011 0.018 0.079 0.001
9

3-methil-1-buten

0.81 445.19 457.43 0.008 0.006 0.009 0.048 0.001
10

cyclobutane

0.85 450.11 462.07 0.000 0.000 0.000 0.002 0.000
11

2-methilpentane

0.96 464.74 474.76 7.571 6.381 8.253 47.296 0.656
12

1-penten

1.11 483.76 489.15 0.018 0.016 0.021 0.115 0.002
13

2-methyl-1-buten

1.18 493.27 495.65 0.033 0.029 0.039 0.216 0.003
14

n-pentane

1.24 500.00 500.00 8.027 6.834 8.839 50.652 0.702
15

trans-2-penten

1.33 504.60 507.51 0.040 0.036 0.047 0.263 0.004
16

cis-2-penten

1.44 509.72 515.29 0.018 0.016 0.022 0.122 0.002
 

···

···

 

···

···

     

···

···

   
320

n-pentadecane

48.26 1500.00 1500.00 0.006 0.007 0.003 0.049 0.000
321

1-hexadecane

50.64 1590.71 1590.93 0.005 0.005 0.002 0.040 0.000
322

n-hexadecane

50.88 1600.00 1600.00 0.008 0.009 0.004 0.065 0.000
 

Total:

      100.000 100.000 100.000 741.178 7.943

Group content

Group

vol% mass% mol% g/l mol/l

Paraffins

24.190 21.227 24.734 157.333 1.965

Iso-paraffins

32.484 29.333 30.100 217.411 2.391

Aromatics

32.548 38.412 34.363 284.700 2.729

Naphtenes

9.253 9.570 9.504 70.933 0.755

Olefins

0.992 0.931 0.963 6.897 0.076

Oxygenates

0.003 0.003 0.004 0.024 0.000

Unknowns

0.530 0.524 0.332 3.880 0.026

Quality parameters

Amount of substance, mol/l:

7.94

Oxygen quantity, mass%:

7.16E-04

Hydrogen quantity, mass%:

1.35E+01

Density, g/l:

741.18

Motor octane number:

77.10

Research octane number:

82.38

Saturation vapour pressure
(using fractional content):

59.949 kPa
(449.66 mm Hg)

Saturation vapour pressure
(using individual content):

62.602 kPa
(469.56 mm Hg)

Fractional content according GOST 2177A

% distillation

boil start 10 50 90 boil end

T distill

40.19 59.11 100.26 155.96 190.46