Relating Thermal Properties to Potential ... - ACS Publications

Dec 14, 2016 - include linseed (flax seed) oil, tung oil, poppy seed oil, perilla ...... Rock-forming Minerals, 2nd ed.; Longman: Harlow, 1992; ISBN 0...
2 downloads 0 Views 696KB Size
Subscriber access provided by GAZI UNIV

Article

Relating Thermal Properties to Potential Interactions between Compounds in Application and Recycling, exemplified by Model Ink-coating Component Mixtures Timo Martti Hartus, and Patrick A. C. Gane Ind. Eng. Chem. Res., Just Accepted Manuscript • DOI: 10.1021/acs.iecr.6b03136 • Publication Date (Web): 14 Dec 2016 Downloaded from http://pubs.acs.org on December 20, 2016

Just Accepted “Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted online prior to technical editing, formatting for publication and author proofing. The American Chemical Society provides “Just Accepted” as a free service to the research community to expedite the dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully peer reviewed, but should not be considered the official version of record. They are accessible to all readers and citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or consequences arising from the use of information contained in these “Just Accepted” manuscripts.

Industrial & Engineering Chemistry Research is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 Published by American Chemical Society. Copyright © American Chemical Society. However, no copyright claim is made to original U.S. Government works, or works produced by employees of any Commonwealth realm Crown government in the course of their duties.

Page 1 of 28

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Industrial & Engineering Chemistry Research

5HODWLQJ 7KHUPDO 3URSHUWLHV WR 3RWHQWLDO ,QWHUDFWLRQV EHWZHHQ &RPSRXQGV LQ $SSOLFDWLRQ DQG 5HF\FOLQJ H[HPSOLILHG E\ 0RGHO ,QN FRDWLQJ &RPSRQHQW 0L[WXUHV 7LPR +DUWXV DQG 3DWULFN $ & *DQH 6FKRRO RI &KHPLFDO 7HFKQRORJ\ 'HSDUWPHQW RI %LRSURGXFWV DQG %LRV\VWHPV $DOWR 8QLYHUVLW\ ),

$DOWR )LQODQG

+DUWXV LV D GRFWRUDO FDQGLGDWH DQG *DQH LV D SURIHVVRU DW WKH 6FKRRO RI &KHPLFDO 7HFKQRORJ\ 'HSDUWPHQW RI %LRSURGXFWV DQG %LRV\VWHPV $DOWR 8QLYHUVLW\ )LQODQG *DQH LV DOVR 9LFH 3UHVLGHQW 6SHFLDO 3URMHFWV 2P\D ,QWHUQDWLRQDO $* &+ 2IWULQJHQ 6ZLW]HUODQG $XWKRU WR ZKRP FRUUHVSRQGHQFH VKRXOG EH VHQW (PDLO WLPR KDUWXV#DDOWR IL 0RELOH SKRQH $%675$&7

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

ACS Paragon Plus Environment

Industrial & Engineering Chemistry Research

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

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

ACS Paragon Plus Environment

Page 2 of 28

Page 3 of 28

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Industrial & Engineering Chemistry Research

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Š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²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

ACS Paragon Plus Environment

Industrial & Engineering Chemistry Research

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

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

ACS Paragon Plus Environment

Page 4 of 28

Page 5 of 28

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Industrial & Engineering Chemistry Research

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

(;3(5,0(17$/ 0DWHULDOV ,Q WKLV VWXG\ PRGHO FRPSRXQGV DQG PRGHO FRPSRXQG PL[WXUHV ZHUH DQDO\VHG 7KH PRGHO FRPSRXQGV ZKLFK KDYH EHHQ DQDO\VHG DUH OLVWHG LQ 7DEOH DQG WKHLU JHQHULF SURSHUWLHV DQG DSSOLFDWLRQV DUH GLVFXVVHG LQ WKH IROORZLQJ 0DWHULDOV IRU PRGHO FRPSRXQG PL[WXUH WKHUPDO DQDO\VLV

7DEOH

*URXS $ 9RODWLOH RLOV

*URXS % 9HJHWDEOH RLOV

0LQHUDO RLO

/LQVHHG RLO 5DSHVHHG RLO

*URXS & 3DSHU FRDWLQJ FRORXU SLJPHQWV *\SVXP .DROLQ 7DOF &D&2 FDOFLXP FDUERQDWH

*URXS ' 3DSHU FRDWLQJ FRORXU DQG LQN ELQGHUV $ON\G UHVLQ 3KHQROLF UHVLQ 6% 6% GULHG ODWH[ $FU\ODWH $FU\ODWH GULHG ODWH[

39$F 39$F GULHG ODWH[ 6WDUFK 0LQHUDO RLO LV D VROYHQW IRU KHDWVHW RIIVHW LQNV E S ƒ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± QRZ 6W\URQ FDOFLXP FDUERQDWH LV D SUHFLSLWDWHG FDOFLXP FDUERQDWH SURGXFW KDYLQJ D SURGXFW QDPH &DORSDNH ) 6SHFLDOW\ 0LQHUDOV ,QF DFU\ODWH $FURQDO 6 9 LV GULHG DQG PLOOHG DFU\ODWH ODWH[ ZKLFK LV D SURGXFW RI %$6) 39$F LV GULHG DQG PLOOHG 39$F ODWH[ 51 ZKLFK LV D SURGXFW RI 5DLVLR &KHPLFDOV 2\ &XUUHQWO\ %$6) LQWHUPHGLDWHO\ &LED DQG 5DLVDP\O 6WDUFK LV D SURGXFW QDPH RI 5DLVLR 2\ &XUUHQWO\ %$6) LQWHUPHGLDWHO\ &LED

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

ACS Paragon Plus Environment

Industrial & Engineering Chemistry Research

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

x x x

FRPSRXQG PL[WXUHV RI WKH FRPSRQHQWV LQ WKH YDULRXV JURXSV YRODWLOH RLOV YHJHWDEOH RLOV SDSHU FRDWLQJ SLJPHQWV DQG SDSHU FRDWLQJ FRORXU DQG LQN ELQGHUV FRPSRXQG PL[WXUHV RI WKH FRPSRQHQWV LQ WKH YDULRXV JURXSV YRODWLOH RLOV YHJHWDEOH RLOV SDSHU FRDWLQJ SLJPHQWV DQG SDSHU FRDWLQJ FRORXU DQG LQN ELQGHUV FRPSRXQG PL[WXUHV RI WKH FRPSRQHQWV LQ WKH YDULRXV JURXSV YRODWLOH RLOV YHJHWDEOH RLOV SDSHU FRDWLQJ SLJPHQWV DQG SDSHU FRDWLQJ FRORXU DQG LQN ELQGHUV

0HWKRGV ,Q WKLV VWXG\ PRGHO FRPSRXQG PL[WXUHV DUH FKDUDFWHULVHG E\ WKHUPDO PHWKRGV WR SURYLGH WKH IROORZLQJ LQIRUPDWLRQ x PDVV ORVV GDWD DV D IXQFWLRQ RI WHPSHUDWXUH x QRQ YRODWLOH UHVLGXXP DW ƒ& x VSHFLILF HQHUJ\ FKDQJHV DV D IXQFWLRQ RI WHPSHUDWXUH DQG ILQDOO\ WKH PDLQ WDUJHW x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

7KHUPRJUDYLPHWULF DQDO\VLV 7KH WKHUPDO ZHLJKW ORVV EHKDYLRXU RI RIIVHW LQN PRGHO FRPSRXQGV DQG LQN SDSHU FRDWLQJ FRORXU PRGHO FRPSRXQG PL[WXUHV ZDV PHDVXUHG DV D IXQFWLRQ RI WHPSHUDWXUH DQG WLPH E\ PHDQV RI WKHUPRJUDYLPHWULF DQDO\VLV XVLQJ D 3HUNLQ (OPHU 7*$ WKHUPRJUDYLPHWULF DQDO\VHU 7KH H[SHULPHQWDOO\ SUREHG WHPSHUDWXUH UHVSRQVH UDQJHG IURP WR ƒ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ƒ& WR ƒ& DW D UDWH RI ƒ& SHU PLQXWH %HIRUH KHDWLQJ WKH VDPSOHV ZHUH VWDELOLVHG DW ƒ& IRU D SHULRG RI RQH PLQXWH 7KH WKHUPDO DQDO\VHV RI WKH PRGHO FRPSRXQGV ZHUH HDFK FDUULHG RXW WZLFH WR HQVXUH UHSURGXFLELOLW\ 7KH GHYLDWLRQ RI WKH WHPSHUDWXUH RI WKH PD[LPXP ZHLJKW ORVVHV 7J$ DFURVV UHSHDWHG VDPSOHV ZDV UHODWLYHO\ VPDOO ± ƒ&

'LIIHUHQWLDO VFDQQLQJ FDORULPHWULF DQDO\VLV 7KHUPDO UHDFWLRQV FDQ EH IROORZHG LQ UHVSHFW WR HQHUJ\ FKDQJHV LQ WKH FORVHG V\VWHP RI WKH VDPSOH ZKLFK FDQ EH PHDVXUHG ZLWK D GLIIHUHQWLDO VFDQQLQJ FDORULPHWULF DQDO\VHU ,Q WKLV VWXG\ D KHDW IOX[ '6& 0HWWOHU 7$ WKHUPDO DQDO\VLV V\VWHP XVLQJ D '6& PHDVXULQJ XQLW ZDV XVHG 7KH H[SHULPHQW WHPSHUDWXUH UDQJHG IURP WR ƒ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ƒ&

ACS Paragon Plus Environment

Page 6 of 28

Page 7 of 28

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Industrial & Engineering Chemistry Research

'6& GHYLFHV PHDVXUH WKH HQHUJ\ ZKLFK LV QHHGHG WR ZDUP D VDPSOH DW D JLYHQ UDWH RU WR D JLYHQ WHPSHUDWXUH RU WR NHHS WKH VDPSOH WHPSHUDWXUH FRQVWDQW RYHU WLPH GXULQJ D WKHUPDO UHDFWLRQ 7KH HQHUJ\ FRQVXPHG RU UHOHDVHG E\ WKH VDPSOH LV IROORZHG DV D IXQFWLRQ RI WHPSHUDWXUH RU WLPH 6ROYHQW HYDSRUDWLRQ DQG PHOWLQJ RI PDWHULDOV DUH HQGRWKHUPLF SKDVH FKDQJHV 7KH GHJUDGDWLRQ RI QRQ YRODWLOH PDWWHU FDXVHV H[RWKHUPLF HQHUJ\ FKDQJHV 7KH SDUDPHWHUV ZKLFK FRXOG EH HYDOXDWHG IURP '6& FXUYHV DUH ƒ HQHUJ\ FKDQJHV GXULQJ VDPSOH KHDWLQJ DQG ƒ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

ACS Paragon Plus Environment

Industrial & Engineering Chemistry Research

7DEOH

3DUDPHWHUV LQ )7,5 PHDVXUHPHQWV

1XPEHU RI VDPSOH VFDQV 1XPEHU RI EDFNJURXQG VFDQV 5HVROXWLRQ FP 6DPSOH JDLQ 0LUURU YHORFLW\ FPV $SHUWXUH VHWWLQJ $ VHWWLQJ RI JLYHV D QRPLQDO DSHUWXUH GLDPHWHU RI

PP DQG DSSUR[LPDWH DUHD RI

FP

5(68/76 $1' ',6&866,216 7KH SURSRUWLRQDO UHOHDVH RI ZDWHU IURP WKH PRGHO FRPSRXQGV DV GHWHFWHG E\ 7J$ DIWHU VWRUDJH LQ DQ DLU FRQGLWLRQHG ODERUDWRU\ DW UHODWLYH KXPLGLW\ 5+ DQG ƒ& WHPSHUDWXUH LV VKRZQ LQ )LJXUH 7KH 7J$ DQDO\VHU ZDV FDOLEUDWHG XVLQJ $OXPHO 1LFNHO DQG 3HUNDOOR\ FDOLEUDWLRQ VWDQGDUGV ZKLFK KDYH PDJQHWLF WUDQVLWLRQ WHPSHUDWXUHV RI ƒ& ƒ& DQG ƒ& UHVSHFWLYHO\ 7KH VHQVLWLYLW\ RI WKH 7J$ LQVWUXPHQW LV —J DQG SUHFLVLRQ 7KH WKHUPDO DQDO\VHV RI WKH PRGHO FRPSRXQGV DQG PRGHO FRPSRXQG PL[WXUHV ZHUH HDFK FDUULHG RXW WZLFH WR HQVXUH UHSURGXFLELOLW\ 7KH GHYLDWLRQ RI WKH WHPSHUDWXUH RI WKH PD[LPXP ZHLJKW ORVVHV 7J$ DFURVV UHSHDWHG VDPSOHV ZDV UHODWLYHO\ VPDOO ± ƒ& îñ îìXñ

}vš vš l9

îì

D}]•šµŒ

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 8 of 28

íñ íîXì íì

ñ íXñ

îXì ìXñ

ìXñ

ìXñ

íXì

îXì

íXñ

íXñ

íXì

ì

)LJXUH

0RLVWXUH FRQWHQW LQ PRGHO FRPSRXQGV DIWHU VWRUDJH DW

5+ DQG

ƒ&

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

ACS Paragon Plus Environment

ƒ& WR

ƒ&

Page 9 of 28

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Industrial & Engineering Chemistry Research

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ƒ& DQG VSHFLILF PHOWLQJ HQHUJ\ -J 7KH VHQVLWLYLW\ RI WKH '6& LQVWUXPHQW LV —: SUHFLVLRQ DQG EDVHOLQH QRLVH “ —: 7KH '6& DQDO\VHV RI WKH VLQJOH PRGHO FRPSRXQGV ZHUH HDFK FDUULHG RXW WZLFH WR HQVXUH UHSURGXFLELOLW\ WKH VSHFLILF HQHUJ\ GHYLDWLRQV ZHUH DERXW 7KH PRGHO FRPSRXQG PL[WXUHV ZHUH DQDO\VHG RQO\ RQFH 7KH GHYLDWLRQ RI WKH UHSHDW VDPSOLQJ RI WKH WHPSHUDWXUH RI WKH PD[LPXP VSHFLILF HQHUJ\ FKDQJHV '6& ZDV VLPLODUO\ WR WKH 7J$ DOVR UHODWLYHO\ VPDOO OHVV WKDQ ƒ& 6RPH LQKRPRJHQHLW\ LQ WKH PL[WXUHV PD\ KDYH DULVHQ LQ WKH JULQGLQJ DQG PL[LQJ VWDJH FDXVLQJ VRPH V\VWHPDWLF TXDQWLWDWLYH HUURU LQ WKH DQDO\VLV LQ WKH FDVH RI DIIHFWHG PRGHO FRPSRXQG PL[WXUHV 7DEOH

6SHFLILF HQHUJ\ FKDQJHV LQ WKH VLQJOH PRGHO FRPSRXQGV

0RGHO FRPSRXQG 6SHFLILF HYDSRUDWLRQ HQHUJ\ DFURVV WKH UDQJH ƒ& -J

6SHFLILF H[RWKHUPDO HQHUJ\ DFURVV WKH UDQJH DW ƒ& -J

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

ACS Paragon Plus Environment

Industrial & Engineering Chemistry Research

(YDSRUDWHG DPRXQW RI PLQHUDO RLO DPRXQW LQ WKH VDPSOH

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

îìì

íìì

D]v Œ o }]o lWs

D]v Œ o }]o l^š Œ Z

• ŒÇo š o š Æ ~ Œ] D]v Œ o }]o l

• D]v Œ o }]o l^ o š Æ ~ Œ]

D]v Œ o }]o lWZ v}o] Œ •]v

D]v Œ o }]o l olÇ Œ •]v

D]v Œ o }]o l'lj•µu

D]v Œ o }]o ld o

D]v Œ o }]o l < }o]v

Œ }v š o ]µu

}]o

v }]o D]v Œ o }]o l^}Ç

D]v Œ o }]o l>]v•

}]o

D]v Œ o }]o l

rïìì

D]v Œ o }]o l Z ‰ •

rîìì

D]v Œ o }]o ~D]v Œ o }]o•

ì

ríìì 6SHFLILF HYDSRUDWLRQ HQHUJ\ -J FDOFXODWHG IRU HYDSRUWHG PDWWHU DW D ƒ& WHPSHUDWXUH UDQJH

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 10 of 28

rðìì

rñìì

ròìì

róìì

rôìì

)LJXUH

(YDSRUDWLRQ TXDQWLW\ RI YRODWLOH PDWHULDO DQG WKH VSHFLILF HYDSRUDWLRQ HQHUJ\ IURP

FRPSRXQG PL[WXUHV

,Q FRPSRXQG PL[WXUHV PLQHUDO RLO NDROLQ DON\G UHVLQ PLQHUDO RLO NDROLQ 6% PLQHUDO RLO WDOF OLQVHHG RLO PLQHUDO RLO WDOF VWDUFK PLQHUDO RLO WDOF 6% PLQHUDO RLO &D&2 6% PLQHUDO RLO &D&2 DON\G PLQHUDO RLO &D&2 OLQVHHG RLO PLQHUDO RLO &D&2 39$F PL[WXUHV )LJXUH DQG PLQHUDO RLO J\SVXP DON\G PLQHUDO RLO J\SVXP OLQVHHG RLO PLQHUDO RLO J\SVXP SKHQROLF UHVLQ PLQHUDO RLO J\SVXP 6% PLQHUDO RLO J\SVXP DFU\ODWH PLQHUDO RLO J\SVXP 39$F PLQHUDO RLO OLQVHHG RLO VWDUFK PLQHUDO RLO SKHQROLF UHVLQ VWDUFK PL[WXUHV )LJXUH KDYH JUHDWHU HYDSRUDWLRQ HQHUJ\ WKDQ VLQJOH PLQHUDO RLO H[FHHGLQJ WKH JUHDWHVW HYDSRUDWLRQ HQHUJLHV RI VWXGLHG FRPSRXQG PL[WXUHV 7KHVH PL[WXUHV DEVRUE D SDUW RI PLQHUDO RLO DQG DOO PLQHUDO RLO GRHV QRW HYDSRUDWH DW WKH WHPSHUDWXUH UDQJH DOVR )LJXUHV

ACS Paragon Plus Environment

)LJXUH rîìì

rïìì ŒÇo š

ŒÇo š

}]o

(YDSRUDWLRQ RI YRODWLOH PDWHULDO DQG VSHFLILF HYDSRUDWLRQ HQHUJ\ IURP rñìì

ACS Paragon Plus Environment

róìì

rôìì

rõìì

ríììì

rííìì

ríîìì

ríïìì

FRPSRXQG PL[WXUHV

Œ }v š l^

}]o

D]v Œ o }]ol

o ]µu

Œ }v š l

ŒÇo š

Œ }v š l^š Œ Z D]v Œ o }]ol

o ]µu

Œ }v š lWs D]v Œ o }]ol o ]µu

Œ }v š lWZ v}o] Œ •]v

Œ }v š l>]v•

Œ }v š l olÇ

o ]µu o ]µu o ]µu o ]µu

D]v Œ o }]ol

ròìì D]v Œ o }]ol

D]v Œ o }]ol

D]v Œ o }]old o l^

D]v Œ o }]old o l^š Œ Z

D]v Œ o }]old o lWs

D]v Œ o }]old o lWZ v}o] Œ •]v

D]v Œ o }]old o l>]v•

D]v Œ o }]old o l olÇ

D]v Œ o }]old o l

D]v Œ o }]ol< }o]vl^

D]v Œ o }]ol< }o]vl

D]v Œ o }]ol< }o]vlWZ v}o] Œ •]v

}]o

D]v Œ o }]ol< }o]vl olÇ D]v Œ o }]ol< }o]vl>]v•

rðìì D]v Œ o }]ol< }o]vl^š Œ Z

ríìì

D]v Œ o }]ol

À ‰}Œ š u}µvš l 9 }( u]v Œ o }]o u}µvš ]v šZ • u‰o

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 ^‰ ](] À ‰}Œ š]}v v ŒPÇ l :Prí ~ o µo š (}Œ À ‰}Œš u šš Œ }À Œ šZ š u‰ Œ šµŒ Œ vP íììr îìì£ •

Page 11 of 28 Industrial & Engineering Chemistry Research

îìì

íìì

ì

Industrial & Engineering Chemistry Research

îìì íìì

ŒÇo š

ŒÇo š

}]ol

D]v Œ o }]olWZ v}o] Œ •]vl

D]v Œ o }]ol>]v•

D]v Œ o }]ol olÇ l ŒÇo š

D]v Œ o }]olWZ v}o] Œ •]vl^

}]ol^ D]v Œ o }]ol>]v•

D]v Œ o }]ol olÇ l^

}]ol^š Œ Z D]v Œ o }]ol>]v•

D]v Œ o }]ol olÇ l^š Œ Z

D]v Œ o }]olWZ v}o] Œ •]vlWs

}]olWs D]v Œ o }]ol>]v•

D]v Œ o }]ol olÇ lWs

ŒÇo š

D]v Œ o }]olWZ v}o] Œ •]vl^š Œ Z

róìì

D]v Œ o }]ol'lj•µul

ròìì

D]v Œ o }]ol'lj•µul^

rñìì

D]v Œ o }]ol'lj•µul^š Œ Z

rðìì

D]v Œ o }]ol'lj•µulWs

rïìì

D]v Œ o }]ol'lj•µulWZ v}o] Œ •]v

rîìì

D]v Œ o }]ol'lj•µul>]v•

ríìì

}]o

ì D]v Œ o }]ol'lj•µul olÇ

À ‰}Œ š u}µvš l 9 }( u]v Œ o }]o u}µvš

ïìì

^‰ ](] À ‰}Œ ]}v v ŒPÇ l :Prí ~ o µo š (}Œ À ‰}Œ š u šš Œ }À Œ šZ š u‰ Œ šµŒ Œ vP íììrîìì £ •

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 12 of 28

rôìì rõìì ríììì rííìì ríîìì ríïìì ríðìì ríñìì ríòìì ríóìì ríôìì ríõìì

)LJXUH

(YDSRUDWLRQ RI YRODWLOH PDWHULDO DQG VSHFLILF HYDSRUDWLRQ HQHUJ\ IURP

FRPSRXQG PL[WXUHV

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

ACS Paragon Plus Environment

À ‰}Œ š u}µvš l 9 }( u]v Œ o }]o

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 ^‰ ](] À ‰}Œ š]}v v ŒPÇ l :Prí ~ o µo š (}Œ À ‰}Œ š u šš Œ }À Œ šZ š u‰ Œ šµŒ Œ vP íììrîìì £ •

)LJXUH ríìì

rîìì

rïìì

rðìì

rñìì

ròìì

róìì

rôìì

rõìì

rííìì Œ }v š l^š Œ Z

Œ }v š lWs

(YDSRUDWLRQ RI YRODWLOH PDWHULDO DQG VSHFLILF HYDSRUDWLRQ HQHUJ\ IURP

ACS Paragon Plus Environment

o ]µu

Œ }v š l^

ríïìì

ríðìì

ríñìì

ríòìì

FRPSRXQG PL[WXUHV

Œ }v š l

ŒÇo š D]v Œ o }]ol olÇ l'lj•µul ŒÇo š

o ]µu

ŒÇo š

D]v Œ o }]ol olÇ l< }o]vl D]v Œ o }]ol olÇ l

ŒÇo š

D]v Œ o }]ol olÇ ld o l

D]v Œ o }]ol olÇ l'lj•µul^

D]v Œ o }]ol olÇ l

D]v Œ o }]ol olÇ l< }o]vl^

D]v Œ o }]ol olÇ ld o l^

D]v Œ o }]ol olÇ l'lj•µul^š Œ Z

D]v Œ o }]ol olÇ l'lj•µulWs

o ]µu

o ]µu

D]v Œ o }]ol olÇ l< }o]vl^š Œ Z

D]v Œ o }]ol olÇ l< }o]vlWs

D]v Œ o }]ol olÇ ld o l^š Œ Z

D]v Œ o }]ol olÇ l

ríîìì D]v Œ o }]ol olÇ l

ríììì D]v Œ o }]ol olÇ ld o lWs

Page 13 of 28 Industrial & Engineering Chemistry Research

îìì

íìì

ì

À ‰}Œ š u}µvš l 9 }( u]v Œ o }]o u}µvš

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 ^‰ ](] À ‰}Œ š]}v v ŒPÇ l :Prí ~ o µo š (}Œ À ‰}Œ š u šš Œ }À Œ šZ š u‰ Œ šµŒ Œ vP íììrîìì £ •

)LJXUH rôìì

(YDSRUDWLRQ RI YRODWLOH PDWHULDO DQG VSHFLILF HYDSRUDWLRQ HQHUJ\ IURP

ACS Paragon Plus Environment }]ol

FRPSRXQG PL[WXUHV

}]ol

ŒÇo š

Œ }v š l

ŒÇo š

ŒÇo š

}]ol< }o]vl ŒÇo š

}]old o l

}]ol'lj•µul

o ]µu D]v Œ o }]ol>]v•

D]v Œ o }]ol>]v•

ríîìì D]v Œ o }]ol>]v•

D]v Œ o }]ol>]v•

Œ }v š l^

}]ol< }o]vl^

}]old o l^

}]ol'lj•µul^

o ]µu D]v Œ o }]ol>]v•

D]v Œ o }]ol>]v•

D]v Œ o }]ol>]v•

D]v Œ o }]ol>]v•

}]ol'lj•µul^š Œ Z

D]v Œ o }]ol>]v•

Œ }v š l^š Œ Z

Œ }v š lWs

}]ol'lj•µulWs

o ]µu

o ]µu

D]v Œ o }]ol>]v•

}]ol

D]v Œ o }]ol>]v•

rííìì }]ol

ríììì

D]v Œ o }]ol>]v•

rõìì }]ol< }o]vl^š Œ Z

róìì

D]v Œ o }]ol>]v•

ròìì }]ol< }o]vlWs

rñìì

D]v Œ o }]ol>]v•

rðìì }]old o l^š Œ Z

rïìì

D]v Œ o }]ol>]v•

rîìì

}]old o lWs

ríìì

D]v Œ o }]ol>]v•

Industrial & Engineering Chemistry Research Page 14 of 28

îìì

íìì

ì

îìì íìì

D]v Œ o }]olWZ v}o] Œ •]vl'lj•µul ŒÇo š

Œ }v š l ŒÇo š o ]µu

D]v Œ o }]olWZ v}o] Œ •]vl< }o]vl ŒÇo š

ŒÇo š D]v Œ o }]olWZ v}o] Œ •]vld o l

D]v Œ o }]olWZ v}o] Œ •]vl'lj•µul^

Œ }v š l^ o ]µu

D]v Œ o }]olWZ v}o] Œ •]vl< }o]vl^

D]v Œ o }]olWZ v}o] Œ •]vld o l^

D]v Œ o }]olWZ v}o] Œ •]vl'lj•µul^š Œ Z

D]v Œ o }]olWZ v}o] Œ •]vl'lj•µulWs

Œ }v š l^š Œ Z

Œ }v š lWs

rííìì

D]v Œ o }]olWZ v}o] Œ •]vl

ríììì

D]v Œ o }]olWZ v}o] Œ •]vl

rõìì

o ]µu

rôìì

D]v Œ o }]olWZ v}o] Œ •]vl

róìì

o ]µu

ròìì

D]v Œ o }]olWZ v}o] Œ •]vl

rñìì

D]v Œ o }]olWZ v}o] Œ •]vl< }o]vl^š Œ Z

rðìì

D]v Œ o }]olWZ v}o] Œ •]vl< }o]vlWs

rïìì

D]v Œ o }]olWZ v}o] Œ •]vld o l^š Œ Z

ríìì

D]v Œ o }]olWZ v}o] Œ •]vld o lWs

ì

rîìì

^‰ ](] À ‰}Œ š]}v v ŒPÇ l :Prí ~ o µo š (}Œ À ‰}Œ š u šš Œ }À Œ šZ š u‰ Œ šµŒ Œ vP íììrîìì £ •

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Industrial & Engineering Chemistry Research

À ‰}Œ š u}µvš l 9 }( u]v Œ o }]o u}µvš ]v šZ • u‰o

Page 15 of 28

ríîìì ríïìì

)LJXUH

(YDSRUDWLRQ RI YRODWLOH PDWHULDO DQG VSHFLILF HYDSRUDWLRQ HQHUJ\ IURP

FRPSRXQG PL[WXUHV

6RPH PL[WXUHV UHWDLQ D PLQRU SDUW RI PLQHUDO RLO LQ SDUWLFXODU VRPH PL[WXUHV FRQWDLQLQJ 6% RU DFU\ODWH ODWH[ RU VWDUFK 7KLV UHWHQWLRQ LV VWURQJHU LI WKH\ DUH LQ D PL[WXUH DGGLWLRQDOO\ FRQWDLQLQJ SKHQROLF UHVLQ OLQVHHG RLO RU UDSHVHHG RLO 3UHYLRXV ZRUNHUV KDYH H[DPLQHG WKH FDSLOODU\ DEVRUSWLRQ RI PLQHUDO RLO DV XVHG LQ RIIVHW SULQWLQJ LQN LQWR PRGHO FRDWLQJ WDEOHW FRPSDFWV FRPSUHVVHG IURP GLVSHUVHG PLQHUDO SLJPHQWV ZLWK D UDQJH RI ODWH[ ELQGHU OHYHOV ,QFUHDVHG SHUPHDELOLW\ IRU VLPLODU FDSLOODULW\ LQFUHDVHG DEVRUSWLRQ UDWH DQG YROXPH OLTXLG XSWDNH G\QDPLF 7KH SUHVHQFH RI ODWH[ OHG WR D UHGXFWLRQ LQ FRQQHFWLYLW\ ZLWKLQ WKH SRUH VWUXFWXUH DQG DQ HIIHFWLYH EODQNLQJ RI DFFHVV WR VRPH SRUHV 6ZHOOLQJ RI WKH SRO\PHU ODWH[ ELQGHU E\ LQWHUSRO\PHU GLIIXVLYH DEVRUSWLRQ RI WKH RLO XVHG UHVXOWHG LQ DGGLWLRQDO IXUWKHU ORQJ WLPHVFDOH ORVV RI FRQQHFWLYLW\ DQG WKXV D JUHDWHU QXPEHU RI LQDFFHVVLEOH SRUHV ,W LV NQRZQ IURP OLWHUDWXUH WKDW ODWH[ RLO GLIIXVLRQ DQG LWV GHSHQGHQW GLVWULEXWLRQ VWURQJO\ DIIHFW LQN VHWWLQJ G\QDPLFV RI WKH SULQW DV WHVWHG E\ IRU H[DPSOH DQ ,QN 6XUIDFH ,QWHUDFWLRQ 7HVWHU ,6,7 D SURGXFW RI 6H*DQ /WG 8. 7KH PXOWLSOH GLIIHUHQFH LQ WKH HIIHFWV REVHUYHG LV VXJJHVWHG WR EH GXH WR WKH IDFW WKDW ORFDOLVHG VXUIDFH DGVRUSWLRQ GHOD\V WKH XSWDNH RI VOLJKWO\ SRODU RLO DQG WKH GLIIXVLYH DEVRUSWLRQ LQWR WKH SRO\PHU PDWUL[ RI ODWLFHV DQG GLVFXVVHG DERYH UHGXFHV SRUH FRQQHFWLYLW\ DQG WKXV VORZV WKH LQN VHWWLQJ G\QDPLF IXUWKHU 7KH UHVXOWDQW FRPELQHG GHOD\HG DEVRUSWLRQ RI WKH VOLJKWO\ SRODU RLOV ZKLFK DFW WR VROYH VRIW UHVLQV LQ WKH LQN EULQJV DERXW D IXUWKHU GHOD\ LQ WKH FRQFHQWUDWLRQ RI WKRVH VROYHG UHVLQV DW WKH LQN FRDWLQJ LQWHUIDFH DQG WKXV DQ DGGLWLRQDO GHOD\ LQ WKH ILQDO ODVW VWDJHV RI LQN VHWWLQJ ,Q WKH REVHUYHG EHKDYLRXU RI FRPSRXQG PL[WXUHV ERXQG ZDWHU LV DJDLQ VHHQ WR HYDSRUDWH WRJHWKHU ZLWK PLQHUDO RLO IURP WKRVH PL[WXUHV FRQWDLQLQJ J\SVXP DQG VWDUFK 7KLV ZDV RQFH DJDLQ SUHGLFWDEOH IURP WKHLU K\JURVFRSLF SURSHUWLHV DQG VWUXFWXUDO ZDWHU FRQWHQW

(QHUJ\ UHOHDVLQJ UHDFWLRQV

ACS Paragon Plus Environment

Industrial & Engineering Chemistry Research

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

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

ACS Paragon Plus Environment

Page 16 of 28

Page 17 of 28

íñì

o µo š (Œ}u šZ u •µŒ •]vPo }u‰}µv À oµ • D •µŒ (Œ}u šZ u]ÆšµŒ •

v ŒPÇ Œ o •

l :Prí

íîì

õì

òì

^‰ ](] ïì

)LJXUH

(QHUJ\ UHOHDVH IURP

FRPSRXQG PL[WXUHV

ACS Paragon Plus Environment

}]ol ŒÇo š Z ‰ •

}]ol^ >]v•

olÇ l^

}]ol^ Z ‰ •

D]v Œ o }]ol^

olÇ lWs

}]ol^š Œ Z >]v•

}]o

}]olWs >]v•

D]v Œ o }]ol>]v•

Œ }v š o ]µu WZ v}o] Œ •]vl

WZ v}o] Œ •]vl< }o]v

}]olWs Z ‰ •

}]olWZ v}o] Œ •]v Z ‰ •

}]ol>]v•

}]o

ì

Z ‰ •

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Industrial & Engineering Chemistry Research

)LJXUH

(QHUJ\ UHOHDVH IURP

FRPSRXQG PL[WXUHV

ACS Paragon Plus Environment o ]µuY

Z ‰ •

}]ol

o ]µuY

ŒÇo š

íñì

}]ol< }o]vl

îìì

Z ‰ •

îñì

ŒÇo š

ïìì

}]old o l

ïñì

Z ‰ •

}]olWZ v}o] Y

Z ‰ •

ŒÇo š

D]v Œ o }]ol o ]µu Œ }v š l^ D]v Œ o }]ol olÇ l ŒÇo š D]v Œ o }]ol>]v• }]ol ŒÇo š

D]v Œ o }]ol< }o]vl^

íñì

}]ol

D]v Œ o }]old o l^

D]v Œ o }]ol>]v• }]ol^

D]v Œ o }]ol olÇ l^

îìì

}]ol>]v•

}]ol olÇ l ŒÇo š

}]ol

}]ol< }o]vl^

}]old o l^

D]v Œ o }]ol>]v• }]ol^š Œ Z D]v Œ o }]olWZ v}o] Œ •]vl^š Œ Z

D]v Œ o }]ol olÇ l^š Œ Z

D]v Œ o }]ol>]v• }]olWs

D]v Œ o }]ol olÇ lWs

l:Prí ïìì

Z ‰ •

Z ‰ •

Z ‰ •

Z ‰ •

Z ‰ •

}]olWZ v}o] Œ •]vl^

}]ol^

}]ol olÇ l^

}]ol>]v•

Z ‰ •

Z ‰ •

o ]µuY

}]ol'lj•µul^š Œ Z

}]ol

}]ol< }o]vlWs

Z ‰ •

Z ‰ •

Z ‰ •

}]ol^š Œ Z

}]olWZ v}o] Œ •]vl^š Œ Z

}]ol>]v•

ì

Z ‰ •

Z ‰ •

Z ‰ •

}]olWZ v}o] Œ •]vlWs

(QHUJ\ UHOHDVH LQ

Z ‰ •

)LJXUH D]v Œ o }]ol olÇ l o ]µuY D]v Œ o }]ol>]v• }]ol o ]µu Œ }v š

ì

}]olWs

D]v Œ o }]ol olÇ ld o

v ŒPÇ Œ o •

^‰ ](] íìì

}]ol>]v•

}]ol olÇ lWs

l:Prí îñì

Z ‰ •

Z ‰ •

v ŒPÇ Œ o •

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

^‰ ](]

Industrial & Engineering Chemistry Research Page 18 of 28

ïñì

o µo š (Œ}u šZ u •µŒ •]vPo }u‰}µv À oµ •

D •µŒ (Œ}u šZ u]ÆšµŒ •

ñì

FRPSRXQG PL[WXUHV

o µo š (Œ}u šZ u •µŒ •]vPo }u‰}µv À oµ • D •µŒ (Œ}u šZ u]ÆšµŒ •

íìì

ñì

)LJXUH (QHUJ\ UHOHDVH IURP FRPSRXQG PL[WXUHV

ACS Paragon Plus Environment >]v•

>]v•

o ]µu

>]v•

>]v•

ŒÇo š

}]ol< }o]vl

Œ }v š l ŒÇo š

ŒÇo š

Œ }v š lWs }]old o l

o ]µu

}]old o lWs

Œ }v š l^

}]ol< }o]vl^

}]old o l^

ŒÇo š

}]ol< }o]vlWs

o ]µu >]v•

>]v•

}]ol

>]v•

>]v•

Œ }v š l

ŒÇo š

olÇ ld o l ŒÇo š

Œ }v š l^

olÇ l< }o]vl^

olÇ ld o l^

olÇ l< }o]vl o ]µu

}]ol

}]ol

>]v•

olÇ l

Œ }v š lWs Œ }v š l^š Œ Z

o ]µu

o ]µu

o ]µu

olÇ l

olÇ l

olÇ l

olÇ l< }o]vl^š Œ Z

olÇ l< }o]vlWs

olÇ ld o l^š Œ Z

v ŒPÇ Œ o •

l:Prí

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

^‰ ](]

Page 19 of 28 Industrial & Engineering Chemistry Research

îìì

íñì

o µo š (Œ}u šZ u •µŒ •]vPo }u‰}µv À oµ •

íìì

D •µŒ (Œ}u šZ u]ÆšµŒ •

ñì

ì

)LJXUH (QHUJ\ UHOHDVH IURP FRPSRXQG PL[WXUHV

ACS Paragon Plus Environment D]v Œ o }]ol>]v•

}]ol

o ]µu

D]v Œ o }]ol>]v•

ŒÇo š ŒÇo š

}]ol< }o]vl Œ }v š l

ŒÇo š

}]old o l D]v Œ o }]ol>]v•

ŒÇo š

}]ol'lj•µul^

D •µŒ

D]v Œ o }]ol olÇ l< }o]vl

D]v Œ o }]ol>]v•

Œ }v š l^

ðì

o ]µu

ôì

}]ol

íìì

D]v Œ o }]ol>]v•

}]ol< }o]vl^

}]old o l^

D]v Œ o }]ol>]v• D]v Œ o }]ol>]v•

Œ }v š l^

o ]µu

D]v Œ o }]ol olÇ l

D]v Œ o }]ol olÇ l< }o]vl^

D]v Œ o }]ol olÇ ld o l^

}]ol'lj•µul^š Œ Z

Œ }v š l^š Œ Z

D]v Œ o }]ol>]v•

o ]µu

Œ }v š lWs

Œ }v š l^š Œ Z

}]ol'lj•µulWs

}]ol

D]v Œ o }]ol>]v•

o ]µu

o ]µu

D]v Œ o }]ol>]v•

}]ol

D]v Œ o }]ol>]v•

D]v Œ o }]ol olÇ l

D]v Œ o }]ol olÇ l< }o]vl^š Œ Z

D]v Œ o }]ol olÇ l< }o]vlWs

D]v Œ o }]ol olÇ ld o l^š Œ Z

v ŒPÇ Œ o •

l:Prí

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 ^‰ ](]

Industrial & Engineering Chemistry Research Page 20 of 28

îìì

íôì

íòì

íðì

íîì

o µo š (Œ}u šZ u •µŒ •]vPo }u‰}µv À oµ •

òì

(Œ}u šZ u]ÆšµŒ •

îì

ì

Page 21 of 28

ïìì

o µo š u •µŒ À oµ •

l:Prí

îñì

(Œ}u šZ •]vPo }u‰}µv

v ŒPÇ Œ o •

îìì

^‰ ](]

D •µŒ (Œ}u šZ u]ÆšµŒ • íñì

íìì

ñì

)LJXUH

(QHUJ\ UHOHDVH IURP

ŒÇo š }]olWZ v}o] Œ •]vl'lj•µul Z ‰ •

ŒÇo š Œ }v š l Z ‰ •

}]olWZ v}o] Œ •]vl

o ]µu

ŒÇo š

}]olWZ v}o] Œ •]vld o l ŒÇo š

}]olWZ v}o] Œ •]vl< }o]vl

Z ‰ •

Z ‰ •

ŒÇo š }]ol'lj•µul }]ol>]v• Z ‰ •

o ]µu

Œ }v š l ŒÇo š }]ol }]ol>]v• Z ‰ •

ŒÇo š

ŒÇo š

}]old o l

}]ol olÇ l< }o]vl

Z ‰ •

}]ol>]v•

ŒÇo š }]ol olÇ l'lj•µul Z ‰ •

Z ‰ •

ŒÇo š Œ }v š l o ]µu }]ol olÇ l Z ‰ •

ŒÇo š }]ol< }o]vl

}]ol olÇ ld o l ŒÇo š Z ‰ •

}]ol>]v• Z ‰ •

}]olWZ v}o] Œ •]vl'lj•µul^ Z ‰ •

Œ }v š l^ o ]µu }]olWZ v}o] Œ •]vl Z ‰ •

}]olWZ v}o] Œ •]vld o l^

}]olWZ v}o] Œ •]vl< }o]vl^

Z ‰ •

Z ‰ •

}]ol'lj•µul^ }]ol>]v• Z ‰ •

Œ }v š l^ Z ‰ •

o ]µu }]ol }]ol>]v•

}]old o l^

}]ol< }o]vl^ }]ol>]v•

}]ol>]v• Z ‰ •

Z ‰ •

}]ol olÇ ld o l^ Z ‰ •

}]ol'lj•µul^š Œ Z }]ol>]v• Z ‰ •

}]ol'lj•µulWs

Œ }v š l^š Œ Z o ]µu }]ol

}]ol>]v• Z ‰ •

}]ol>]v• Z ‰ •

}]ol>]v• Z ‰ •

}]ol< }o]vlWs

}]ol>]v•

}]old o l^š Œ Z

ì

Z ‰ •

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Industrial & Engineering Chemistry Research

FRPSRXQG PL[WXUHV

1RQ YRODWLOH UHVLGXXP 7KH FRPSRVLWLRQ RI WKH PL[WXUH DIIHFWV WKH DPRXQW RI QRQ YRODWLOH UHVLGXXP DIWHU WKHUPDO GHJUDGDWLRQ 1DWXUDOO\ PRVW RI WKH QRQ YRODWLOH PDWHULDO LQ WKH PL[WXUHV LV LQRUJDQLF SLJPHQW 7KH FRPSRXQG PL[WXUHV SURGXFH WKH JUHDWHVW DPRXQW RI QRQ YRODWLOH UHVLGXXP LQ 7J$ 3UREDEOH S\URO\VLV RFFXUV LQ VRPH FDVHV 7KH DQG FRPSRXQG PL[WXUHV KDG RQO\ PLQRU HIIHFWV RQ WKH UHVLGXXP LQ 7J$ FRPSDUHG ZLWK WKH FDOFXODWHG UHVLGXXP IURP VLQJOH FRPSRXQG YDOXHV %RWK ZDWHU DQG R[\JHQ FRQWHQW

ACS Paragon Plus Environment

Industrial & Engineering Chemistry Research

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

óì

òì

E}vrÀ}o š]o Œ •] µ ~(Œ}u dP }( šZ u]ÆšµŒ •• l 9 }( • u‰o

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 22 of 28

ñì

ðì Kï l Ws ïì WZ v}o] Œ •]v l

olÇ l

îì

ŒÇo š

ŒÇo š

>]v•

}]o l 'lj•µu

ÇAÆ íì

ì

ì

íì

îì

E}vrÀ}o š]o Œ •] µ ~ o µo š )LJXUH

ïì

ðì

(Œ}u šZ dP }( šZ •]vPo

1RQ YRODWLOH UHVLGXXP RI WZR FRPSRXQG PL[WXUHV DIWHU 7J$

ACS Paragon Plus Environment

ñì

}u‰}v ••l 9 }( • u‰o

òì

Page 23 of 28

òì }]o l < }o]v l^

>]v•

olÇ l d o lWs

E}vrÀ}o š]o Œ •] µ ~(Œ}u dP }( šZ u]ÆšµŒ •• l 9 }( • u‰o

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Industrial & Engineering Chemistry Research

ñì

ðì

ïì Z ‰ •

}]o l olÇ l

Z ‰ •

ŒÇo š

}]o l WZ v}o] Œ •]v l Ws

îì

D]v Œ o }]o l d o l Ws

ÇAÆ

íì

ì

ì

ñ

íì

íñ

îì

E}vrÀ}o š]o Œ •] µ ~ o µo š )LJXUH

îñ

ïì

(Œ}u dP }( šZ •]vPo

ïñ

ðì

ðñ

}u‰}µv ••l 9 }( • u‰o

1RQ YRODWLOH UHVLGXXP RI WKUHH FRPSRXQG PL[WXUHV DIWHU 7J$

ACS Paragon Plus Environment

ñì

Industrial & Engineering Chemistry Research

òì

D]v Œ o }]o l olÇ l d o l ^ E}vrÀ}o š]o Œ •] µ ~(Œ}u dP }( u]ÆšµŒ •• l9 }( • u‰o

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 24 of 28

ñì

}]o l olÇ l d o l

Z ‰ •

D]v Œ o }]o l olÇ l 'lj•µu l

ŒÇo š

ŒÇo š

ðì

D]v Œ o }]o l olÇ l

Kï l

ŒÇo š

ïì

îì

íì

Z ‰ •

}]o l WZ v}o] Œ •]v l

ÇAÆ

Kï l

D]v Œ o }]o l >]v•

ŒÇo š }]o l

Kï l Ws

ì ì

ñ

íì

E}vrÀ}o š]o Œ •] µ ~ o µo š

)LJXUH

íñ

(Œ}u dP }( •]vPo

îì

îñ

ïì

}u‰}µv • }( • u‰o

1RQ YRODWLOH UHVLGXXP RI IRXU FRPSRXQG PL[WXUHV DIWHU 7J$

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

ACS Paragon Plus Environment

Page 25 of 28

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Industrial & Engineering Chemistry Research

)7,5 DQDO\VHG QRQ YRODWLOH UHVLGXXP &RPELQHG UHVLGXXP LQ VLQJOH FRPSRXQGV FRPSDUHG ZLWK WKH UHVLGXXP LQ WKH PL[WXUHV DQG WKRVH VKRZLQJ WKH JUHDWHVW PDVV GHYLDWLRQV ZHUH DQDO\VHG ZLWK WKH )7,5 VSHFWURPHWHU $V DQ H[DPSOH )7,5 VSHFWUXP RI 5DSHVHHG RLO $ON\G $FU\ODWH PL[WXUH DIWHU 7J$ LV SUHVHQWHG LQ )LJXUH 7KH VHOHFWHG PL[WXUHV KDYH EHHQ PDUNHG ZLWK DUURZV LQ )LJXUHV DQG 7KH UHVLGXD ZHUH DQDO\VHG IURP .%U WDEOHWV EHFDXVH RI WKH VPDOO VDPSOH DPRXQW Å PJ UHPDLQLQJ DIWHU WKHUPDO WUHDWPHQW 7KH )7,5 VSHFWUD HQDEOH RQH WR SURYLGH VRPH LQWHUSUHWDWLRQV 7KH PRVW VLJQLILFDQW EDQGV IURP WKH VSHFWUD DUH FROOHFWHG LQ 6XSSRUWLQJ LQIRUPDWLRQ LQ 7DEOHV 6 6 ,Q WKH FRPSRXQG PL[WXUHV ERWK SKHQROLF UHVLQ DQG DON\G LQ PL[WXUH ZLWK DFU\ODWH KDYH LQFUHDVHG UHVLGXXP DIWHU 7J$ FRPSDUHG ZLWK WKHLU FRPELQHG UHVLGXXP RI WKH VLQJOH FRPSRXQGV )LJXUH 2EVHUYHG EDQGV DUH PDLQO\ WKH VDPH DV LQ WKH VLQJOH FRPSRXQGV ,Q PL[WXUHV WKH\ FDQ EH FRQGHQVHG DV D VORZO\ GHJUDGLQJ DQG HYDSRUDWLQJ IRUP 2EVHUYHG )7,5 EDQGV LQ &D&2 39$F PL[WXUH DUH SUREDEO\ IURP FDOFLXP FDUERQDWH ZKLFK PD\ EH SDUWO\ GHFRPSRVHG WR &D2 LQ DFLGLF PL[WXUH GXULQJ WKH WKHUPDO WUHDWPHQW *\SVXP ORVHV ERXQG ZDWHU DW HOHYDWHG WHPSHUDWXUH %DQGV DQG FP DUH GXH WR &D62 7KH SHDN DW FP PD\ LQGLFDWH VRPH FRQGHQVHG HVWHU VWUXFWXUH IURP OLQVHHG RLO 7DEOH

)LJXUH

)7,5 VSHFWUXP RI 5DSHVHHG RLO $ON\G $FU\ODWH PL[WXUH DIWHU 7J$

,Q WKH FRPSRXQG PL[WXUHV 7DEOH UDSHVHHG RLO DON\G DFU\ODWH UDSHVHHG RLO SKHQROLF UHVLQ 39$F DON\G WDOF 39$F DQG OLQVHHG RLO NDROLQ 6% PL[WXUHV KDYH LQFUHDVHG QRQ YRODWLOH UHVLGXXP LQ PL[WXUHV FRPSDUHG ZLWK WKH FRPELQHG VLQJOH FRPSRXQG UHVLGXD )LJXUH 7KHUH PD\ EH S\URO\VHG RU FRQGHQVHG QRQ YRODWLOH SURGXFWV ,Q WKH )7,5 VSHFWUD D VWURQJ EDQG DW DERXW FP LV GXH ZDWHU UHVLGXD $OVR WKH SUHVHQFH RI FDUER[\ODWH LRQV KDV DEVRUSWLRQ SHDN DW DERXW FP %DQGV DW Å FP FDQ EH DVVLJQHG WR FDUER[\OLF JURXS MRLQHG ZLWK DONHQH RU DU\O JURXSV 7ZR DEVRUSWLRQ SHDNV WKH UDQJH WR FP ZKLFK DUH SUREDEO\ VWUHWFKLQJ IUHTXHQFLHV RI VLQJOH ERQGV RI FDUERQ WR K\GURJHQ DUH IRXQG LQ WKH )7,5 VSHFWUD RI WKH UHVSHFWLYH REVHUYHG FRPSRXQG PL[WXUHV /LQVHHG RLO NDROLQ 6% DQG PLQHUDO RLO WDOF 39$F PL[WXUHV KDYH GHFUHDVHG QRQ YRODWLOH UHVLGXXP LQ PL[WXUHV FRPSDUHG ZLWK WKHLU FRPELQHG VLQJOH FRPSRXQG UHVLGXD )LJXUH &KDUDFWHULVWLF EDQGV LQ WKH )7,5 VSHFWUD RI WDOF DQG NDROLQ FDQ EH

ACS Paragon Plus Environment

Industrial & Engineering Chemistry Research

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 26 of 28

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±PL[WXUH WZR EDQGV DW DQG FP PD\ LQGLFDWH DURPDWLF VWUXFWXUHV IRUPHG LQ WKH 7J$ :DWHU DEVRUSWLRQ IUHTXHQWO\ GLVWXUEV )7,5 PHDVXUHPHQWV

:DWHU FDQ EH VHHQ DV D EURDG EDQG RYHU

FP

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ƒ& 0LQHUDO SLJPHQWV DUH JHQHUDOO\ WKHUPDOO\ VWDEOH RYHU WKH DSSOLFDWLRQ WHPSHUDWXUH UDQJH LQ SUDFWLFH

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

ACS Paragon Plus Environment

Page 27 of 28

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Industrial & Engineering Chemistry Research

7KH VWURQJHVW HQHUJ\ UHOHDVLQJ LQWHUDFWLRQ ZDV IRXQG LQ WKH PL[WXUH RI OLQVHHG RLO DQG VWDUFK 7KH K\JURVFRS\ RI WKH VWDUFK VXJJHVWHG LW ZLOO UHDFW ZLWK VOLJKWO\ SRODU RLOV OLNH UDSHVHHG DQG OLQVHHG RLO

6833257,1* ,1)250$7,21 1RQ YRODWLOH UHVLGXXP RI WKH PL[WXUHV DIWHU 7J$ 6SHFWUDO PD[LPD 7DEOHV IURP )7,5 VSHFWUD RI WKH PRGHO FRPSRXQGV 6SHFWUDO PD[LPD 7DEOHV IURP )7,5 VSHFWUD RI VWXGLHG PRGHO FRPSRXQG PL[WXUHV DIWHU 7J$

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