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Department of Chemistry John R. Lindsay Smith, Moray S. Stark, Julian J. Wilkinson Department of Chemistry, University of York, York YO10 5DD, UK Peter M. Lee, Martin Priest School of Mechanical Engineering, University of Leeds, Leeds, LS2 9JT, UK R. Ian Taylor Shell Global Solutions, Shell Research Ltd., Chester, CH1 3SH, UK Simon Chung Infineum UK Ltd., Milton Hill, Abingdon, Oxfordshire, OX13 6BB, UK The Degradation of Lubricants in Gasoline Engines STLE Annual Meeting : Toronto 17 th - 20 th May 2004

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Page 1: Department of Chemistry John R. Lindsay Smith, Moray S. Stark, Julian J. Wilkinson Department of Chemistry, University of York, York YO10 5DD, UK Peter

Department of Chemistry

John R. Lindsay Smith, Moray S. Stark, Julian J. WilkinsonDepartment of Chemistry, University of York, York YO10 5DD, UK

Peter M. Lee, Martin PriestSchool of Mechanical Engineering, University of Leeds, Leeds, LS2 9JT, UK

R. Ian TaylorShell Global Solutions, Shell Research Ltd., Chester, CH1 3SH, UK

Simon ChungInfineum UK Ltd., Milton Hill, Abingdon, Oxfordshire, OX13 6BB, UK

The Degradation of Lubricants in Gasoline Engines

STLE Annual Meeting : Toronto 17th- 20th May 2004

Page 2: Department of Chemistry John R. Lindsay Smith, Moray S. Stark, Julian J. Wilkinson Department of Chemistry, University of York, York YO10 5DD, UK Peter

Department of Chemistry

John R. Lindsay Smith, Moray S. Stark, Julian J. Wilkinson*Department of Chemistry, University of York, York YO10 5DD, UK

Peter M. Lee, Martin PriestSchool of Mechanical Engineering, University of Leeds, Leeds, LS2 9JT, UK

R. Ian TaylorShell Global Solutions, Chester, CH1 3SH, UK

Simon ChungInfineum UK Ltd., Milton Hill, Abingdon, Oxfordshire, OX13 6BB, UK

The Degradation of Lubricants in Gasoline Engines

Julian Wilkinson [email protected] www.york.ac.uk/res/gkg

Part 3: Chemical Mechanisms for the Oxidation of Branched Alkanes

Page 3: Department of Chemistry John R. Lindsay Smith, Moray S. Stark, Julian J. Wilkinson Department of Chemistry, University of York, York YO10 5DD, UK Peter

Department of Chemistry

Aims

Identify products from micro-reactor oxidation.

Compare results to engine.Use identified products to propose

reaction mechanisms.Ultimately, understand and predict

viscosity increase

Page 4: Department of Chemistry John R. Lindsay Smith, Moray S. Stark, Julian J. Wilkinson Department of Chemistry, University of York, York YO10 5DD, UK Peter

Department of Chemistry

Aims

Page 5: Department of Chemistry John R. Lindsay Smith, Moray S. Stark, Julian J. Wilkinson Department of Chemistry, University of York, York YO10 5DD, UK Peter

Department of Chemistry

Chemical Mechanisms for the Oxidation of Branched Alkanes

Previous Work

Branched Alkanes as Base Fluid Models

Chemical Analyses

Reaction Mechanisms

Page 6: Department of Chemistry John R. Lindsay Smith, Moray S. Stark, Julian J. Wilkinson Department of Chemistry, University of York, York YO10 5DD, UK Peter

Department of Chemistry

Summary of oxidation

Sludge

L ac tones A lcohols K etones Bifunc tiona ls A c ids

Hydroperox ide

A lkane

?

Viscosity Increase

Page 7: Department of Chemistry John R. Lindsay Smith, Moray S. Stark, Julian J. Wilkinson Department of Chemistry, University of York, York YO10 5DD, UK Peter

Department of Chemistry

Traditional Model of Hydrocarbon Oxidation

+ ROO . .+ ROOH

Alkane Alkyl radical

Page 8: Department of Chemistry John R. Lindsay Smith, Moray S. Stark, Julian J. Wilkinson Department of Chemistry, University of York, York YO10 5DD, UK Peter

Department of Chemistry

Traditional Model of Hydrocarbon Oxidation

+ ROO. .

+ ROOH

.+ O2

OO Alkane Alkyl radical

Hydroperoxy radical

Page 9: Department of Chemistry John R. Lindsay Smith, Moray S. Stark, Julian J. Wilkinson Department of Chemistry, University of York, York YO10 5DD, UK Peter

Department of Chemistry

Traditional Model of Hydrocarbon Oxidation

+ ROO. .

+ ROOH

.+ O2

OO

OO

+ RH

OO

H

+ R.

Alkane Alkyl radical

Hydroperoxy radical

Hydroperoxide

Page 10: Department of Chemistry John R. Lindsay Smith, Moray S. Stark, Julian J. Wilkinson Department of Chemistry, University of York, York YO10 5DD, UK Peter

Department of Chemistry

Traditional Model of Hydrocarbon Oxidation

OO

H

O

+ .OH

Hydroperoxide Alkoxy radical

Page 11: Department of Chemistry John R. Lindsay Smith, Moray S. Stark, Julian J. Wilkinson Department of Chemistry, University of York, York YO10 5DD, UK Peter

Department of Chemistry

Traditional Model of Hydrocarbon Oxidation

OO

H

O

O + H

O

+ RH

OH

+ R.

Alkoxy radical Alcohol

Page 12: Department of Chemistry John R. Lindsay Smith, Moray S. Stark, Julian J. Wilkinson Department of Chemistry, University of York, York YO10 5DD, UK Peter

Department of Chemistry

Traditional Model of Hydrocarbon Oxidation

O

+ H2O

OO

H

Hydroperoxide Ketone

Page 13: Department of Chemistry John R. Lindsay Smith, Moray S. Stark, Julian J. Wilkinson Department of Chemistry, University of York, York YO10 5DD, UK Peter

Department of Chemistry

Ease of abstraction of H atom

C

H

H

H

C

C

C

C

C

C

C

H

C

H

HH

H H

H

H

H

HH

H

H

H H

Page 14: Department of Chemistry John R. Lindsay Smith, Moray S. Stark, Julian J. Wilkinson Department of Chemistry, University of York, York YO10 5DD, UK Peter

Department of Chemistry

Ease of abstraction of H atom

Page 15: Department of Chemistry John R. Lindsay Smith, Moray S. Stark, Julian J. Wilkinson Department of Chemistry, University of York, York YO10 5DD, UK Peter

Department of Chemistry

Ease of abstraction of H atom

H Primary: Difficult

Page 16: Department of Chemistry John R. Lindsay Smith, Moray S. Stark, Julian J. Wilkinson Department of Chemistry, University of York, York YO10 5DD, UK Peter

Department of Chemistry

Ease of abstraction of H atom

H

H

Primary: Difficult

Secondary: Moderately difficult

Page 17: Department of Chemistry John R. Lindsay Smith, Moray S. Stark, Julian J. Wilkinson Department of Chemistry, University of York, York YO10 5DD, UK Peter

Department of Chemistry

Ease of abstraction of H atom

H

H

H

Primary: Difficult

Secondary: Moderately difficult

Tertiary: Easy

Page 18: Department of Chemistry John R. Lindsay Smith, Moray S. Stark, Julian J. Wilkinson Department of Chemistry, University of York, York YO10 5DD, UK Peter

Department of Chemistry

Ease of abstraction of H atom

H

H

H

H

Primary: Difficult

Secondary: Moderately difficult

Allylic: Very easy

Tertiary: Easy

Page 19: Department of Chemistry John R. Lindsay Smith, Moray S. Stark, Julian J. Wilkinson Department of Chemistry, University of York, York YO10 5DD, UK Peter

Department of Chemistry

Models of Hydrocarbon Base-Fluids

No. of Carbons

XHVI™ 8.2 (average) 39(random example)

Page 20: Department of Chemistry John R. Lindsay Smith, Moray S. Stark, Julian J. Wilkinson Department of Chemistry, University of York, York YO10 5DD, UK Peter

Department of Chemistry

Models of Hydrocarbon Base-Fluids

No. of Carbons

XHVI™ 8.2 (average) 39

Trimethylheptane 10

(random example)

Page 21: Department of Chemistry John R. Lindsay Smith, Moray S. Stark, Julian J. Wilkinson Department of Chemistry, University of York, York YO10 5DD, UK Peter

Department of Chemistry

Trimethylheptane Oxidation : 100 – 120 °C

OO H

OO

H

OO

OO

H

O

O

H

D. E. Van Sickle, J. Org. Chem., 37, 755 1972

Page 22: Department of Chemistry John R. Lindsay Smith, Moray S. Stark, Julian J. Wilkinson Department of Chemistry, University of York, York YO10 5DD, UK Peter

Department of Chemistry

Trimethylheptane Oxidation : 100 – 120 °C

OO H

OO

H

OO

OO

H

O

O

H

OO

H

O

O

H

OO

H

D. E. Van Sickle, J. Org. Chem., 37, 755 1972

Page 23: Department of Chemistry John R. Lindsay Smith, Moray S. Stark, Julian J. Wilkinson Department of Chemistry, University of York, York YO10 5DD, UK Peter

Department of Chemistry

Trimethylheptane Oxidation : 100 – 120 °C

OO H

OO

H

OO

OO

H

O

O

H

OO

H

O

O

H

OO

H

D. E. Van Sickle, J. Org. Chem., 37, 755 1972O O

HH

O O O

H H H

Page 24: Department of Chemistry John R. Lindsay Smith, Moray S. Stark, Julian J. Wilkinson Department of Chemistry, University of York, York YO10 5DD, UK Peter

Department of Chemistry

Models of Hydrocarbon Base-Fluids

No. of Carbons

XHVI™ 8.2 (average) 39

Trimethylheptane 10

Hexadecane 16

(random example)

Page 25: Department of Chemistry John R. Lindsay Smith, Moray S. Stark, Julian J. Wilkinson Department of Chemistry, University of York, York YO10 5DD, UK Peter

Department of Chemistry

Hexadecane Oxidation : 120 – 180 °C

Jensen et al, J. Am. Chem. Soc., 103, 1742 1981 and 101, 7574 1979

OO H

Page 26: Department of Chemistry John R. Lindsay Smith, Moray S. Stark, Julian J. Wilkinson Department of Chemistry, University of York, York YO10 5DD, UK Peter

Department of Chemistry

Hexadecane Oxidation : 120 – 180 °C

Jensen et al, J. Am. Chem. Soc., 103, 1742 1981 and 101, 7574 1979

OO H

OO

H

OO

Page 27: Department of Chemistry John R. Lindsay Smith, Moray S. Stark, Julian J. Wilkinson Department of Chemistry, University of York, York YO10 5DD, UK Peter

Department of Chemistry

Hexadecane Oxidation : 120 – 180 °C

Jensen et al, J. Am. Chem. Soc., 103, 1742 1981 and 101, 7574 1979

OO H

OO

H

OO

OO

H

OO

H

Page 28: Department of Chemistry John R. Lindsay Smith, Moray S. Stark, Julian J. Wilkinson Department of Chemistry, University of York, York YO10 5DD, UK Peter

Department of Chemistry

Hexadecane Oxidation : 120 – 180 °C

Jensen et al, J. Am. Chem. Soc., 103, 1742 1981 and 101, 7574 1979

OO H

OO

H

OO

OO

H

OO

H

O OH

Page 29: Department of Chemistry John R. Lindsay Smith, Moray S. Stark, Julian J. Wilkinson Department of Chemistry, University of York, York YO10 5DD, UK Peter

Department of Chemistry

Models of Hydrocarbon Base-Fluids

No. of Carbons

XHVI™ 8.2 (average)

39 Trimethylheptane

10

Hexadecane

16

Tetramethylpentadecane

19

(random example)

(TMPD)

Page 30: Department of Chemistry John R. Lindsay Smith, Moray S. Stark, Julian J. Wilkinson Department of Chemistry, University of York, York YO10 5DD, UK Peter

Department of Chemistry

Models of Hydrocarbon Base-Fluids

No. of Carbons

XHVI™ 8.2 (average)

39

Trimethylheptane 10

Hexadecane

16

TMPD

19

Squalane 30

(random example)

Page 31: Department of Chemistry John R. Lindsay Smith, Moray S. Stark, Julian J. Wilkinson Department of Chemistry, University of York, York YO10 5DD, UK Peter

Department of Chemistry

Amount of Tertiary Carbons in a Range of Base Fluids

0

5

10

15

20

25

PA

O

Gro

up II

I iso

dew

axed

Gro

up II

I hyd

rocr

acke

dG

roup

IIG

roup

IX

HV

I 8.2

tert

iary

C (

%)

McKenna et al. STLE Annual Meeting, Houston, 2002

Page 32: Department of Chemistry John R. Lindsay Smith, Moray S. Stark, Julian J. Wilkinson Department of Chemistry, University of York, York YO10 5DD, UK Peter

Department of Chemistry

Amount of Tertiary Carbons in a Range of Base Fluids

0

5

10

15

20

25

terti

ary

C (%

)

McKenna et al. STLE Annual Meeting, Houston, 2002

Page 33: Department of Chemistry John R. Lindsay Smith, Moray S. Stark, Julian J. Wilkinson Department of Chemistry, University of York, York YO10 5DD, UK Peter

Department of Chemistry

Oxidation of TMPD

time (min)

Micro-reactor conditions: 1000 mbar O2, 200 ºC, 1 minute

GC-MS conditions: ZB-5 column, 50-300 ºC, 6 ºC min-1

impurity

Page 34: Department of Chemistry John R. Lindsay Smith, Moray S. Stark, Julian J. Wilkinson Department of Chemistry, University of York, York YO10 5DD, UK Peter

Department of Chemistry

Oxidation of TMPD: Ketones

time (min)

O

(m/e = +14)

Ketone

impurity

Page 35: Department of Chemistry John R. Lindsay Smith, Moray S. Stark, Julian J. Wilkinson Department of Chemistry, University of York, York YO10 5DD, UK Peter

Department of Chemistry

Oxidation of TMPD: Ketones

time (min)

O

(m/e = +14)

O

O

O

Page 36: Department of Chemistry John R. Lindsay Smith, Moray S. Stark, Julian J. Wilkinson Department of Chemistry, University of York, York YO10 5DD, UK Peter

Department of Chemistry

Oxidation of TMPD: Alkanes

time (min)

Alkane

Page 37: Department of Chemistry John R. Lindsay Smith, Moray S. Stark, Julian J. Wilkinson Department of Chemistry, University of York, York YO10 5DD, UK Peter

Department of Chemistry

Oxidation of TMPD: Fragmentation

time (min)

O

O

+ .

RH

Page 38: Department of Chemistry John R. Lindsay Smith, Moray S. Stark, Julian J. Wilkinson Department of Chemistry, University of York, York YO10 5DD, UK Peter

Department of Chemistry

Oxidation of TMPD: Fragmentation

time (min)

+

O

O

Page 39: Department of Chemistry John R. Lindsay Smith, Moray S. Stark, Julian J. Wilkinson Department of Chemistry, University of York, York YO10 5DD, UK Peter

Department of Chemistry

Oxidation of TMPD : Fragmentation

time (min)

+

O

O

Page 40: Department of Chemistry John R. Lindsay Smith, Moray S. Stark, Julian J. Wilkinson Department of Chemistry, University of York, York YO10 5DD, UK Peter

Department of Chemistry

Oxidation of TMPD : Alkenes

time (min)

Page 41: Department of Chemistry John R. Lindsay Smith, Moray S. Stark, Julian J. Wilkinson Department of Chemistry, University of York, York YO10 5DD, UK Peter

Department of Chemistry

Possible Mechanisms of Alkene Formation

OHH

OH+

Page 42: Department of Chemistry John R. Lindsay Smith, Moray S. Stark, Julian J. Wilkinson Department of Chemistry, University of York, York YO10 5DD, UK Peter

Department of Chemistry

Possible Mechanisms of Alkene Formation

OH

O

OH

+ (H+)

OO

+ H2O

Alcohol AcidEster

Page 43: Department of Chemistry John R. Lindsay Smith, Moray S. Stark, Julian J. Wilkinson Department of Chemistry, University of York, York YO10 5DD, UK Peter

Department of Chemistry

Possible Mechanisms of Alkene Formation

OO

OH

O

+

Acid

Ester

Alkene

Page 44: Department of Chemistry John R. Lindsay Smith, Moray S. Stark, Julian J. Wilkinson Department of Chemistry, University of York, York YO10 5DD, UK Peter

Department of Chemistry

Alkenes and viscosity increase

Very Easy .

Monomer

Page 45: Department of Chemistry John R. Lindsay Smith, Moray S. Stark, Julian J. Wilkinson Department of Chemistry, University of York, York YO10 5DD, UK Peter

Department of Chemistry

Alkenes and viscosity increase

.

+ .

• Alkenes could cause large viscosity increase.

Dimer (sludge precursor)

Page 46: Department of Chemistry John R. Lindsay Smith, Moray S. Stark, Julian J. Wilkinson Department of Chemistry, University of York, York YO10 5DD, UK Peter

Department of Chemistry

Oxidation of TMPD : Alcohols

time (min)OH OH

OH

OH

Solvent (MeOH)

Conditions: Carbowax column, 50-250 ºC, 4 ºC min-1

Page 47: Department of Chemistry John R. Lindsay Smith, Moray S. Stark, Julian J. Wilkinson Department of Chemistry, University of York, York YO10 5DD, UK Peter

Department of Chemistry

Alcohols and viscosity increase

Alkanes

Weak interactions

Page 48: Department of Chemistry John R. Lindsay Smith, Moray S. Stark, Julian J. Wilkinson Department of Chemistry, University of York, York YO10 5DD, UK Peter

Department of Chemistry

Alcohols and viscosity increase

OH

OH

Alcohols may cause modest viscosity increase

Strong interactions (Hydrogen bonding)

Page 49: Department of Chemistry John R. Lindsay Smith, Moray S. Stark, Julian J. Wilkinson Department of Chemistry, University of York, York YO10 5DD, UK Peter

Department of Chemistry

Oxidation of Squalane

Micro-reactor conditions: 1000 mbar O2, 200 ºC, 2 mins

GC conditions: ZB-5 column, 50-300 ºC, 6 ºC min-1

Time (mins)

Page 50: Department of Chemistry John R. Lindsay Smith, Moray S. Stark, Julian J. Wilkinson Department of Chemistry, University of York, York YO10 5DD, UK Peter

Department of Chemistry

Products of Squalane Oxidation in Micro-Reactor: Ketones

O

O

O

O

Time (mins)

Page 51: Department of Chemistry John R. Lindsay Smith, Moray S. Stark, Julian J. Wilkinson Department of Chemistry, University of York, York YO10 5DD, UK Peter

Department of Chemistry

Products of Squalane Oxidation in the Micro-Reactor

+ Isomers

Time (mins)

Alkane

Alkene

Page 52: Department of Chemistry John R. Lindsay Smith, Moray S. Stark, Julian J. Wilkinson Department of Chemistry, University of York, York YO10 5DD, UK Peter

Department of Chemistry

Oxidation of TMPD : Fragmentation

.

time (min)

O

O

+

RH

O2

Page 53: Department of Chemistry John R. Lindsay Smith, Moray S. Stark, Julian J. Wilkinson Department of Chemistry, University of York, York YO10 5DD, UK Peter

Department of Chemistry

Oxidation of TMPD : Carboxylic acids

O

OH

O

OH

GC Conditions: FFAP column, 50-250 ºC4 ºC min-1

Time (mins)

Page 54: Department of Chemistry John R. Lindsay Smith, Moray S. Stark, Julian J. Wilkinson Department of Chemistry, University of York, York YO10 5DD, UK Peter

Department of Chemistry

Reactions of Primary Alkyl Radicals : Formation of Carboxylic Acids

OO

H O

HH

OH+

Page 55: Department of Chemistry John R. Lindsay Smith, Moray S. Stark, Julian J. Wilkinson Department of Chemistry, University of York, York YO10 5DD, UK Peter

Department of Chemistry

Reactions of Primary Alkyl Radicals : Formation of Carboxylic Acids

O

H

H

O

- .

Page 56: Department of Chemistry John R. Lindsay Smith, Moray S. Stark, Julian J. Wilkinson Department of Chemistry, University of York, York YO10 5DD, UK Peter

Department of Chemistry

Reactions of Primary Alkyl Radicals : Formation of Carboxylic Acids

O

O2

O

OO

. .

Page 57: Department of Chemistry John R. Lindsay Smith, Moray S. Stark, Julian J. Wilkinson Department of Chemistry, University of York, York YO10 5DD, UK Peter

Department of Chemistry

Reactions of Primary Alkyl Radicals : Formation of Carboxylic Acids

O

OO

O

OOH

. RH

O

OOH

O

OH

Page 58: Department of Chemistry John R. Lindsay Smith, Moray S. Stark, Julian J. Wilkinson Department of Chemistry, University of York, York YO10 5DD, UK Peter

Department of Chemistry

Oxidation of Squalane: Carboxylic acid detection by GC-MS

Carboxylic acids are difficult to detect directly by GC-MS.

Have been converted to esters.

O

OH

O

OMe

MeOH

H+

Carboxylic acid Ester

Page 59: Department of Chemistry John R. Lindsay Smith, Moray S. Stark, Julian J. Wilkinson Department of Chemistry, University of York, York YO10 5DD, UK Peter

Department of Chemistry

Oxidation of Squalane: Carboxylic acid detection by GC-MS

O

O

.O

OHO2

O

OMe

Detected by GC-MS

methylated

Page 60: Department of Chemistry John R. Lindsay Smith, Moray S. Stark, Julian J. Wilkinson Department of Chemistry, University of York, York YO10 5DD, UK Peter

Department of Chemistry

Oxidation of Squalane : Formation of Carboxylic Acids and Ketones (Infra-red spectroscopy)

Ketone peak Acid peak

Page 61: Department of Chemistry John R. Lindsay Smith, Moray S. Stark, Julian J. Wilkinson Department of Chemistry, University of York, York YO10 5DD, UK Peter

Department of Chemistry

Oxidation of Squalane : Formation of Carboxylic Acids and Ketones (Infra-red spectroscopy)

Ketone peak

After washing with KOH (aq)

Page 62: Department of Chemistry John R. Lindsay Smith, Moray S. Stark, Julian J. Wilkinson Department of Chemistry, University of York, York YO10 5DD, UK Peter

Department of Chemistry

XHVI™ 8.2 Oxidation in Engine

Conditions : Sump Oil Samples, 2000 rpm, 50 % throttleLubricant : XHVITM 8.2, 2 % (w/w) sulfonate detergent

0

2

4

6

8

0 20 40 60 80Time (hours)

Con

cent

ratio

n (1

0-3

mol

/ lit

re)

Total Carbonyl

Page 63: Department of Chemistry John R. Lindsay Smith, Moray S. Stark, Julian J. Wilkinson Department of Chemistry, University of York, York YO10 5DD, UK Peter

Department of Chemistry

Oxidation in Engine : Carbonyl vs. Acid

Conditions : Sump Oil Samples, 2000 rpm, 50 % loadLubricant : XHVITM 8.2, 2 % (w/w) sulfonate detergent

0

2

4

6

8

0 20 40 60 80Time (hours)

Con

cent

ratio

n (1

0-3

mol

/ lit

re)

Carboxylic AcidTotal Carbonyl

Page 64: Department of Chemistry John R. Lindsay Smith, Moray S. Stark, Julian J. Wilkinson Department of Chemistry, University of York, York YO10 5DD, UK Peter

Department of Chemistry

Carboxylic Acid : Total Carbonyl Ratio

0

20

40

60

80

100

0 20 40 60 80Time (hours)

[Ca

rbox

ylic

Aci

d]

[

Tota

l Ca

rbon

yl]

(%

)

Conditions : Sump Oil Samples, 2000 rpm, 50 % throttleLubricant : XHVITM 8.2, 2 % w/w sulfonate detergent

Page 65: Department of Chemistry John R. Lindsay Smith, Moray S. Stark, Julian J. Wilkinson Department of Chemistry, University of York, York YO10 5DD, UK Peter

Department of Chemistry

Squalane oxidation: Engine Test

Squalane + detergent was used as the lubricant in Ricardo-Hydra engine.

Samples collected from the sump and ring-pack.

Page 66: Department of Chemistry John R. Lindsay Smith, Moray S. Stark, Julian J. Wilkinson Department of Chemistry, University of York, York YO10 5DD, UK Peter

Department of Chemistry

Squalane oxidation: Engine Test

0.00

0.10

0.20

0.30

0.40

0.50

0.60

0.70

0.80

0 50 100 150 200 250

Time (mins)

Co

nce

ntr

atio

n (

10-3

Mo

l/litr

e)

carb

on

yl

squalane

XHVI

Page 67: Department of Chemistry John R. Lindsay Smith, Moray S. Stark, Julian J. Wilkinson Department of Chemistry, University of York, York YO10 5DD, UK Peter

Department of Chemistry

Conclusions

Radical abstraction mainly occurs at tertiary sites. Alkenes very significant, possible sludge

precursors. Alcohols could give modest viscosity increase. Not predicted by previous work on model base

fluids

Page 68: Department of Chemistry John R. Lindsay Smith, Moray S. Stark, Julian J. Wilkinson Department of Chemistry, University of York, York YO10 5DD, UK Peter

Department of Chemistry

Conclusions

Radical abstraction mainly occurs at tertiary sites. Alkenes very significant, possible sludge

precursors. Alcohols could give modest viscosity increase. Not predicted by previous work on model base

fluids

Acknowledgements

Shell Global Solutions


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