)JOEBXJ 1VCMJTIJOH $PSQPSBUJPO

+PVSOBM PG $IFNJTUSZ
7PMVNF  "SUJDMF *%   QBHFT
IUUQEYEPJPSH

3FTFBSDI "SUJDMF
*OUFSBDUJPO PG /BUVSBM %ZF $OOLXP FHSD
XJUI *POJD 4VSGBDUBOUT

4IBMJOJ $IBOESBWBOTIJ BOE 4BOUPTI , 6QBEIZBZ

%FQBSUNFOU PG $IFNJTUSZ )BSDPVSU #VUMFS 5FDIOPMPHJDBM *OTUJUVUF /BXBCHBOK ,BOQVS  *OEJB

$PSSFTQPOEFODF TIPVME CF BEESFTTFE UP 4BOUPTI , 6QBEIZBZ VQBEIZBZ@T@L!SFEJČNBJMDPN

3FDFJWFE  +VOF  "DDFQUFE  "VHVTU 

"DBEFNJD &EJUPS +PÑM 'MFVSFODF

$PQZSJHIU ª  4 $IBOESBWBOTIJ BOE 4 , 6QBEIZBZ ćJT JT BO PQFO BDDFTT BSUJDMF EJTUSJCVUFE VOEFS UIF $SFBUJWF $PNNPOT
"UUSJCVUJPO -JDFOTF XIJDI QFSNJUT VOSFTUSJDUFE VTF EJTUSJCVUJPO BOE SFQSPEVDUJPO JO BOZ NFEJVN QSPWJEFE UIF PSJHJOBM XPSL JT
QSPQFSMZ DJUFE

"MMJVN DFQB JT B OBUVSBM EZF UIBU IBT CFFO FYUSBDUFE GSPN POJPO TLJO XJUI UIF IFMQ PG TPYIMFU BQQBSBUVT ćF QJHNFOU JO UIF EZF
QFMBSHPOJEJO XBT GPVOE UP CF   ćF JOUFSBDUJPO PG UIF EZF XJUI JPOJD TVSGBDUBOUT OBNFMZ DBUJPOJD TVSGBDUBOU DFUZMUSJNFUIZ
MBNNPOJVN CSPNJEF
BOE BOJPOJD TPEJVN MBVSZM TVMQIBUF
IBT CFFO TUVEJFE CZ TQFDUSPQIPUPNFUSJDBMMZ DPOEVDUJWJUZ BOE TVSGBDF
UFOTJPO NFBTVSFNFOUT ćF UIFSNPEZOBNJD BOE TVSGBDF QBSBNFUFST IBWF CFFO FWBMVBUFE GPS UIF JOUFSBDUJPO QSPDFTT ćF SFTVMUT
JOEJDBUF \TVSGBDUBOUEZF^ DPNQMFY GPSNBUJPO BOE EPNJOBUJPO PG BETPSQUJPO JO DPNQBSJTPO UP NJDFMMJ[BUJPO

 *OUSPEVDUJPO EZFJOH QSPDFTT TVDI BT UFYUJMFT EZFJOH QIPUPHSBQIZ BOE JO

QIBSNBDFVUJDBMT QSPDFTTFT
4ZOUIFUJD EZFT BMNPTU IBWF UIFJS PSJHJO GSPN DPBM UBS UIBU ćF TUVEJFT PO UIF JOUFSBDUJPO CFUXFFO OBUVSBM EZFT BOE
MFBET UP UIF GPSNBUJPO PG IBSNGVM BUNPTQIFSJD HBTFT <> TVSGBDUBOUT BSF JNQPSUBOU BOE JOUFSFTUJOH GPS JNQSPWJOH UIF
4FWFSBM TZOUIFUJD DPMPSBOUT IBWF CFFO CBOOFE CFDBVTF UIFZ EZFJOH QSPDFTT GSPN UIFPSFUJDBM UFDIOPMPHJDBM FDPMPHJDBM
DBVTF BMMFSHJD FČFDUT /BUVSBM EZFT BSF EFSJWFE GSPN OBUV BOE FDPOPNJDBM QPJOUT PG WJFX )PXFWFS OPU NVDI BUUFOUJPO
SBMMZ PDDVSSJOH TPVSDFT TVDI BT QMBOUT JOTFDUT BOJNBMT BOE IBT CFFO NBEF PO UIF JOUFSBDUJPO CFUXFFO OBUVSBM EZFT BOE
NJOFSBMT /BUVSBM EZFT BSF HFOFSBMMZ FDPGSJFOEMZ BOE DBO TVSGBDUBOUT 3FDFOUMZ UIF JOUFSBDUJPO CFUXFFO TPNF OBUVSBM
QSPWJEF B XJEF SBOHF PG CFBVUJGVM TIBEFT XJUI BDDFQUBCMF EZFT 3VCJB DPSEJGPMJB BOE 1VOJDB HSBOBUVN
XJUI BOJPOJD BOE
MFWFMT PG DPMPS GBTUOFTT <o> " OVNCFS PG DPNNFSDJBM EZFT DBUJPOJD TVSGBDUBOUT IBT CFFO NBEF BOE UIF SFTVMUT XFSF GPVOE
BOE UFYUJMFT NJMMTQMBOUT TUBSUFE MPPLJOH BU UIF QPTTJCJMJUJFT UP CF FODPVSBHJOH <> ćFSFGPSF JU XBT XPSUIXIJMF UP NBLF
PG VTJOH OBUVSBM EZFT UP PWFSDPNF FOWJSPONFOUBM QPMMVUJPO GVSUIFS TUVEJFT JOWPMWJOH TPNF NPSF OBUVSBM EZFT
DBVTFE CZ TZOUIFUJD EZFT 7BSJPVT SFQPSUT <o> IBWF CFFO *O UIF QSFTFOU DPNNVOJDBUJPO UIF SFTVMUT PG JOUFSBDUJPO
BQQFBSFE PO UIF CFIBWJPS BOE BQQMJDBUJPOT PG UIF OBUVSBM EZFT PG BMMJVN DFQB EZF XJUI DBUJPOJD TVSGBDUBOU DFUZMUSJNFUIZ
PO UFYUJMFT MBNNPOJVN CSPNJEF
BOE BOJPOJD TVSGBDUBOU TPEJVN MBVSZM
4VSGBDUBOUT DPOUBJOJOH CPUI IZESPQIJMJD BOE IZESPQIPCJD TVMQIBUF
BSF SFQPSUFE
NPJFUJFT BSF FYUFOTJWFMZ VTFE JO PVS EBJMZ MJGF BOE BMTP JO
WBSJPVT JOEVTUSJBM QSPDFTTFT TVDI BT UFYUJMFT QVMQ BOE QBQFS
JOEVTUSZ ćF VTF PG XBUFS BT B NFEJVN GPS UFYUJMF QSPDFTTJOH  &YQFSJNFOUBM ćF FYUSBDUJPO PG EZF QJHNFOU XBT GPM
JEFBMMZ SFRVJSFT MJRVJE UIBU XFUT UIF ĕCFS TVSGBDF RVJDLMZ BOE MPXFE BT EFTDSJCFE CZ ½OBM <> 0OJPO TLJO EZF BMMJVN
VOJGPSNMZ BOE IFSF TVSGBDUBOUT QMBZ B VTFGVM SPMF CFDBVTF DFQB
XBT FYUSBDUFE CZ TPYIMFU BQQBSBUVT 4VSGBDUBOUT TVDI
UIFTF DBO CF VTFE BT MFWFMJOH EJTQFSTJOH BOE XFUUJOH BHFOUT BT TPEJVN MBVSZM TVMQIBUF BOE DFUZMUSJNFUIZMBNNPOJVN
4VSGBDUBOUT BSF SFRVJSFE GPS MFWFM EZFJOH BOE TP PO <o> CSPNJEF ćPNBT CBLFS .VNCBJ *OEJB
XFSF VTFE BT TVDI
ćF TVSGBDUBOUT BDU NPTUMZ JO UXP XBZT FJUIFS UIFZ DBO GPSN )PXFWFS UIF DSJUJDBM NJDFMMF DPODFOUSBUJPO $.$
PG CPUI
B DPNQMFY XJUI JPOJD EZFT PS UIFZ DBO CF BETPSCFE JOUP UIF UIF TVSGBDUBOUT XBT EFUFSNJOFE CZ DPOEVDUJWJUZ BT XFMM BT
ĕCFS 4VSGBDUBOUEZF BTTPDJBUJPOT BSF JNQPSUBOU JO WBSJPVT TVSGBDF UFOTJPO NFBTVSFNFOU BOE XBT GPVOE UP CF  š −
 +PVSOBM PG $IFNJTUSZ

5ĮįĹIJ  4QFDUSPTDPQJD EBUB GPS UIF JOUFSBDUJPO PG EZFT XJUI TVSGBD  $POEVDUJWJUZ .FBTVSFNFOU ćF TQFDJĕD DPOEVDUJWJUZ
UBOUT BU ○ $ L
PG B TFSJFT PG TPMVUJPOT PG TVSGBDUBOU BOE NJYUVSF PG
4VSGBDUBOU ಮNBY BOE BCTPSCBODF PG EZF  H-
TVSGBDUBOU XJUI EZF BU DPOTUBOU UFNQFSBUVSF  t ○ $
XFSF
4VSGBDUBOU BEEFE NFBTVSFE PO BO BVUPNBUJD DPOEVDUJWJUZ NFUFS 4ZTUSPOJD
ಮNBYt "CTPSCBODF

H-
ON
t BU ಮNBY
*OEJB
XJUI B DPOEVDUJWJUZ DFMMUZQF $% XJUI QMBUJOVN
FMFDUSPEF FNCFEEFE JO HMBTT BOE IBWJOH DFMM DPOTUBOU PG
/JM    DN−  ćF 4QFDJĕD $POEVDUJWJUZ
WFSTVT <4VSGBDUBOU> QMPU
/B-4    TIPXFE UXP TUSBJHIU MJOFT XJUI EJČFSFOU TMPQFT ćF $.$ PG
   TVSGBDUBOU XBT EFUFSNJOFE GSPN UIF QPJOU PG JOUFSTFDUJPO PG
   UIFTF UXP TUSBJHIU MJOFT
  
$5"#     4VSGBDF 5FOTJPO .FBTVSFNFOU ćF TVSGBDF UFOTJPO PG
   BRVFPVT TPMVUJPOT PG JOEJWJEVBM TVSGBDUBOU BOE EZFNJYFE
TVSGBDUBOU XFSF NFBTVSFE BU ○ $ VTJOH UIF 8JMIFMNZ QMBUF
NFUIPE PO B UFOUJPNFUFS %$"5 %BUF 1IZTJDT (FSNBOZ

HO
+ ćF PCTFSWFE TVSGBDF UFOTJPO ದ
PG B TPMVUJPO XBT QMPUUFE
O
OH BHBJOTU MPH <4VSGBDUBOU> ćF QMPU TIPXFE UXP TUSBJHIU MJOFT
XJUI EJČFSFOU TMPQFT ćF $.$ PG UIF TPMVUJPO XBT EFUFS
NJOFE GSPN UIF QPJOU PG JOUFSTFDUJPO PG UXP TUSBJHIU MJOFT
OH
 3FTVMUT BOE %JTDVTTJPO
OH  &MFDUSPOJD 677JTJCMF 4QFDUSB ćF BCTPSCBODF PG UIF
FYUSBDUFE TBNQMFT XBT NFBTVSFE BU UIF XBWFMFOHUI SBOHJOH
o ON ćF TQFDUSVN PG POJPO TLJO EZF "MMJVN DFQB

4İĵIJĺIJ  JO BCTFODF BOE JO QSFTFODF PG TVSGBDUBOUT UIBU JT DBUJPOJD

TVSGBDUBOU DFUZMUSJNFUIZM BNNPOJVN CSPNJEF
BOE BOJPOJD
TVSGBDUBOU TPEJVN MBVSZM TVMQIBUF
IBT CFFO PCTFSWFE ćF
BOE  š − NPM EN− JO DBTF PG $5"# <> BOE /B-4 SFTVMUT BSF TIPXO JO 'JHVSF  ćF BWFSBHF WBMVFT PG ಮQE\ BOE
<> SFTQFDUJWFMZ "MM UIF TPMVUJPOT VTFE JO UIF FYQFSJNFOU BSF BCTPSCBODF BU ಮQE\ UBLFO GSPN UISFF SFQFBUFE FYQFSJNFOUT
QSFQBSFE VTJOH EPVCMFEJTUJMMFE XBUFS GSPN BMLBMJOF ,.O0  BSF HJWFO JO 5BCMF 
*U DBO CF TFFO UIBU PO BEEJUJPO PG /B-4 UIF ಮQE\ TIJęFE
 &YUSBDUJPO .FUIPE 0OJPO TLJO PG LOPXO XFJHIU XBT GSPN  ON UP  ON UIBU JT UPXBSET MPOHFS XBWFMFOHUI
NJODFE ćFO UIF NJODFE POJPO TLJO XBT XSBQQFE QSPQFSMZ XIJMF BEEJUJPO PG $5"# SFTVMUT JO B TIJę PG ಮQE\ GSPN
JO FYUSBNJDSPQPSF ĕMUFS QBQFS GPS  IS GPS UIF SFNPWBM PG  ON UP  ON "O JODSFBTF JO BCTPSCBODF JOUFOTJUZ XBT
NPJTUVSF JG QSFTFOU 4PYIMFU BQQBSBUVT XBT VTFE UP FYUSBDU BMTP PCTFSWFE PO JODSFBTJOH UIF BNPVOU PG TVSGBDUBOUT JO
UIF EZFTUVČ GSPN UIF POJPO TLJO "CTPMVUF NFUIBOPM PG BCPVU EZF TPMVUJPO 5BCMF 
 ćF SFTVMUT DMFBSMZ JOEJDBUF BO BTTP
 NM XBT BEEFE UP UIF NJODFE POJPO TLJO UIFO USBOTGFSSFE DJBUJPODPNQMFYBUJPO CFUXFFO EZF BOE TVSGBDUBOUT "T UIF
JOUP 4PYIMFU BQQBSBUVT GPS  IS ćFSFBęFS UIF TPMWFOU XBT NPMFDVMBS XFJHIUT PG UIF OBUVSBM EZF DPVME OPU CF DBMDVMBUFE
FWBQPSBUFE VTJOH SPUBUPSZ FWBQPSBUPS GPS IBMG BO IPVS BOE EVF UP WBSJPVT DPOTUJUVFOUT QSFTFOU JO EZF UIF EFUBJM TUVEZ PG
UIFO ESJFE EZF XBT PCUBJOFE BOE XFJHIFE ćF BNPVOU PG UIF DPNQMFY GPSNFE EVF UP JOUFSBDUJPO PG EZF BOE TVSGBDUBOU
QFMBSHPOJEJO QJHNFOU JO EZF PG EBSL SFE DPMPS
XBT GPVOE DPVME OPU CF JOWFTUJHBUFE
UP CF  
 ćFSNPEZOBNJD 1BSBNFUFST CZ $POEVDUJWJUZ .FUIPE *O
 $PMPSJOH 1JHNFOU JO %ZF ćF TLJO PG UIF POJPO JT JOFEJCMF PSEFS UP DPOTJEFS UIF FČFDU PG EZF PO UIF $.$ PG UIF
"MMJVN DFQB
BOE JU DPOUBJOT B EZFTUVČ DBMMFE QFMBSHPOJEJO TVSGBDUBOUT UIF TQFDJĕD DPOEVDUJWJUZ PG B TFSJFT PG TPMVUJPO JO
    UFUSBIZESPYZ BOUIPDZBOJEJO
4DIFNF 
 BCTFODF BOE JO QSFTFODF PG EJČFSFOU BNPVOU PG EZF JO TPMVUJPO
1FMBSHPOJEJO IBT GPVS IZESPYZM HSPVQT BMM PG XIJDI BSF NJYUVSF IBT CFFO NFBTVSFE ćF SFTVMUT BSF HJWFO JO UIF GPSN
BVYPDISPNF HSPVQT TVDI BT /) $00) $POTFRVFOUMZ PG UIF QMPU PG 4QFDJĕD $POEVDUJWJUZ
WFSTVT <4VSGBDUBOU> JO
QFMBSHPOJEJO FYIJCJUT HPPE EZFJOH QSPQFSUJFT GPS UIF EZFJOH 'JHVSFT  BOE  JO DBTF PG /B-4 BOE $5"# SFTQFDUJWFMZ
PG XPPM BOE TP GPSUI "T TVDI UIFTF GPVS BVYPDISPNF HSPVQT ćF WBMVFT PG $.$ PG /B-4 BOE $5"# JO BCTFODF BOE JO
GPSN UIF TUBCMF DPNQMFY DPNQPVOE XIJDI JT CFTU GPS XPPM QSFTFODF PG EJČFSFOU BEEFE BNPVOU PG EZF BSF HJWFO JO 5BCMF
EZFJOH  *U JT PCTFSWFE UIBU PO JODSFBTJOH BNPVOU PG EZF JO BRVFPVT
TVSGBDUBOU TPMVUJPO UIF $.$ PG UIF TVSGBDUBOU EFDSFBTFT
 4QFDUSPQIPUPNFUSJD 4UVEJFT ćF TQFDUSPTDPQJD NFBTVSF ćF EFHSFF PG DPVOUFS JPO EJTTPDJBUJPO ಥ
XBT PCUBJOFE CZ
NFOUT XFSF DBSSJFE PVU PO B WJTJCMF TQFDUSPQIPUPNFUFS UIF SBUJP PG UIF TMPQF PG UIF QPTUNJDFMMBS SFHJPO 4
UP UIBU
5741 5PTIOJXBM *OEJB
BOE 67 EPVCMFCFBN TQFD PG QSFNJDFMMBS SFHJPO 4
 ćF PCTFSWFE SFHVMBS JODSFBTF JO
USPQIPUPNFUFS  4ZTUSPOJDT *OEJB
 EFHSFF PG DPVOUFS JPO EJTTPDJBUJPO PO EZF BEEJUJPO 5BCMF 

+PVSOBM PG $IFNJTUSZ 

5ĮįĹIJ  ćFSNPEZOBNJD QBSBNFUFST GPS UIF JOUFSBDUJPO PG EZFT XJUI TVSGBDUBOUT BU ○ $ CZ DPOEVDUJWJUZ NFUIPE

<%ZF> iಥw
$.$ −əৼ○NJD t  əਈ○NJD t  ə৽○NJD t 
4VSGBDUBOU BEEFE %FHSFF PG DPVOUFS
NPM EN−
L+ NPM−
+,− NPM−
L+ NPM−

H-
JPO EJTTPDJBUJPO
/JM  š −    −
$5"#   š −    −
 H-
  š −    −
  š −    −
/JM  š −    −
/B-4   š −    
 H-
  š −    −
  š −    −

0.6 0.6

4QFDJĕD DPOEVDUJWJUZ ঴ NIPT

0.5 0.5

0.4 0.4 d
Absorbance

c
b
0.3 a
0.3
0.2
0.2
0.1 c
b 0.1
a

510 520 530 540 550 560 570 580 590 600 0
঳ ON
2.2 4.4 6.6 8.8 11 13.2 15.4 17.6 19.8
4 −3
[CTAB] ×10 (mol dm )
'ĶĴłĿIJ  1MPUT PG "CTPSCBODF
WFSTVT XBWFMFOHUI ಮ
BU ○ $ JO
DBTF PG "MMJVN EZF B SFQSFTFOUT QMPU JO BCTFODF PG TVSGBDUBOU C BOE 'ĶĴłĿIJ  1MPUT PG 4QFDJĕD $POEVDUJWJUZ
WFSTVT <$5"#> BU ○ $ B
D BSF JO QSFTFODF PG  HM PG /B-4 BOE $5"# SFTQFDUJWFMZ "MMJVN C D BOE E BSF JO QSFTFODF PG /JM   BOE  HM EZF SFTQFDUJWFMZ
EZF   HM

0.6 XIFSF i಼w JT UIF əਈ○ NJD

BOE TUBOEBSE FOUSPQZ DIBOHF
ə৽○ NJD
GPS UIF NJDFMMF NPMBS DPODFOUSBUJPO PG XBUFS UIBU
4QFDJĕD DPOEVDUJWJUZ ঴ NIPT

0.5 JT  BU ○ $ ਇ =  + NPM− ,− BOE ਉ JT UFNQFSBUVSF

d JO ,FMWJO
c
0.4 ba 'VSUIFS UIF TUBOEBSE FOUSPQZ DIBOHF GPSNBUJPO XBT
0.3 DBMDVMBUFE VTJOH UIF GPMMPXJOH SFMBUJPOT <>
ਓ (əৼ○ NJD )
0.2 əਈ○ NJD = −  

ਓਢ
0.1
əৼ○ NJD = ə৽○ NJD − ਉəਈ○ NJD  

0
2.8 4.8 6.8 8.8 10.8 12.8 14.8 16.8 18.8 *O 5BCMF  UIF WBMVFT PG UIFSNPEZOBNJD QBSBNFUFST OBNFMZ
3 −3 əৼ○ NJD ə৽○ NJD BOE əਈ○ NJD JO CPUI UIF DBTFT UIBU JT JOUFSBD
[NaLS] ×10 (mol dm )
UJPO PG EZF XJUI /B-4 BOE $5"# BSF SFQPSUFE ćF OFHBUJWJUZ
'ĶĴłĿIJ  1MPUT PG 4QFDJĕD $POEVDUJWJUZ
WFSTVT </B-4> BU ○ $ B PG WBMVFT PG əৼ○ NJD JO FBDI DBTF GBWPST UIF NJDFMMJ[BUJPO
C D BSF JO QSFTFODF PG /JM   BOE  HM SFTQFDUJWFMZ ćF WBMVF PG əৼ○ NJD CFDPNFT NPSF OFHBUJWF BU IJHIFS EZF
DPOUFOU JOEJDBUJOH NJDFMMJ[BUJPOBHHSFHBUJPO CFDPNFT NPSF
GBWPSBCMF BU IJHIFS EZF DPOUFOU ćF QPTJUJWF FOUSPQZ DIBOHF
JT QSPCBCMZ EVF UP BO JODSFBTF JO UIF DIBSHFE EFOTJUZ BU UIF əਈ○ NJD
VQPO BHHSFHBUJPO JT NBKPS DPOUSJCVUJPO UP UIF
NJDFMMF TVSGBDF OFHBUJWF WBMVFT PG GSFF FOFSHZ DIBOHF əৼ○ NJD
BOE UIVT JT
ćF TUBOEBSE (JCCT GSFF FOFSHZ GPS UIF NJDFMMF GPSNBUJPO UIF NBJO ESJWJOH GPSDF SFTQPOTJCMF GPS UIF BHHSFHBUJPO ćF
əৼ○ NJD
XBT PCUBJOFE CZ VTJOH GPMMPXJOH SFMBUJPO <> FOUSPQZ UIBU JODSFBTFT PO NJDFMMJ[BUJPO JO BRVFPVT NFEJVN
IBT CFFO FYQMBJOFE FJUIFS J
PO UIF CBTJT PG TUSVDUVSJOH PG
UIF XBUFS NPMFDVMFT TVSSPVOEJOH UIF IZESPDBSCPO DIBJOT JO
əৼ○ NJD =  ਇਉ (PSK $.$ − PSK ಼)  
BRVFPVT NFEJVN SFTVMUJOH JO BO JODSFBTF JO UIF FOUSPQZ PG
 +PVSOBM PG $IFNJTUSZ

5ĮįĹIJ  4VSGBDF QBSBNFUFST GPS JOUFSBDUJPO PG EZFT XJUI TVSGBDUBOUT BU ○ $ CZ TVSGBDF UFOTJPO NFBTVSFNFOU

"SFB QFS
4VSGBDF FYDFTT
<%ZF> NPMFDVMF BU
$.$ DPODFOUSBUJPO −əৼ○BE t  əਈ○BE t  ə৽○BE t 
4VSGBDUBOU BEEFE JOUFSGBDF Q$ $.$$
NPM EN−
ɘ š  L+ NPM−
+,− NPM−
+ NPM−

H-
ਐਡ
NPM DN−

"○

/JM  š −       
$5"#   š −      − 
 H-
  š −      − 
  š −      − 
/JM  š −      − 
/B-4   š −      − 
 H-
  š −      − 
  š −      − 

90 80

80 70

Surface tension (dyn/cm)

Surface tension (dyn/cm)

70
60
60
50
50 a a
b b
c 40 c
40 d d
30
30
0
0
3.8 3.6 3.4 3.2 3 2.8 2.6 2.4 2 1.8
2.8 2.6 2.4 2.2 2 1.8 1.6 1.4
log[CTAB]
log[NaLS]

'ĶĴłĿIJ  1MPUT PG 4VSGBDF 5FOTJPO

WFSTVT MPH </B-4> BU ○ $ B C 'ĶĴłĿIJ  1MPUT PG 4VSGBDF 5FOTJPO
WFSTVT MPH <$5"#> BU ○ $ B
D BOE E BSF TBNF BT JO 'JHVSF  C D BOE E BSF UIF TBNF BT JO 'JHVSF 

UIF TZTUFN XIFO UIF IZESPDBSCPO DIBJOT BSF SFNPWFE GSPN EFUFSNJOFE BU ○ $ ćF TVSGBDF UFOTJPO PG /B-4 BOE $5"#
UIF BRVFPVT NFEJVN UP UIF JOUFSJPS PG NJDFMMF PS JJ
PO UIF JO BCTFODF BOE QSFTFODF PG WBSZJOH BEEFE BNPVOU PG EZF
CBTJT PG JODSFBTFE GSFFEPN PG UIF IZESPQIPCJD DIBJO JO UIF JT SFQSFTFOUFE BT 4VSGBDF 5FOTJPO
WFSTVT MPH <4VSGBDUBOU>
OPOQPMBS JOUFSJPS PG UIF NJDFMMF DPNQBSFE UP UIF BRVFPVT 'JHVSFT  BOE  JO DBTF PG /B-4 BOE $5"# SFTQFDUJWFMZ
FOWJSPONFOU ćF WBMVFT PG $.$ BU EJČFSFOU BEEJUJWF EZF PCUBJOFE GSPN
ćF XBUFS NPMFDVMFT BSPVOE UIF IZESPDBSCPO DIBJO GPSN CSFBL QPJOU PG 4VSGBDF 5FOTJPO
WFSTVT MPH <TVSGBDUBOU> BSF
B TPMWBUJPO MBZFS EVSJOH UIF EJTTPMVUJPO PG TVSGBDUBOU JO XBUFS HJWFO JO 5BCMF  " EFDSFBTF JO $.$ PO JODSFBTJOH UIF
ćVT EVF UP GPSNBUJPO PG TPMWBUJPO MBZFS XJUI IJHIMZ PSEFSFE EZF DPODFOUSBUJPO IBT CFFO PCTFSWFE JO CPUI UIF DBTFT ćF
XBUFS NPMFDVMFT UIF FOUSPQZ PG UIF TZTUFN JODSFBTFT NBLJOH SFEVDUJPO JO TVSGBDF UFOTJPO PO BEEJUJPO PG EZF JOEJDBUFT
UIF EJTTPMVUJPO PG UIF IZESPDBSCPO DIBJOT IJHIMZ VOGBWPSBCMF UIF GPSNBUJPO PG \EZFTVSGBDUBOU^ DPNQMFY EVF UP CJOEJOH PG
ćF BHHSFHBUJPO PG TVSGBDUBOU JOUP NJDFMMFT XJUIJO XIJDI TVSGBDUBOU XJUI EZF
UIF IZESPDBSCPO DIBJOT BSF MPDBUFE JO UIF JOUFSJPS BOE UIF ćF DPODFOUSBUJPO PG UIF TVSGBDUBOU BU UIF JOUFSGBDF NBZ
NPMFDVMFT BSF BODIPSFE BU UIF JOUFSGBDF CZ IZESPQIJMJD IFBE CF DBMDVMBUFE GSPN TVSGBDF PS JOUFSGBDJBM EBUB CZ UIF VTF PG
HSPVQT SFNBJOJOH JO DPOUBDU XJUI XBUFS
IPXFWFS EFDSFBTFT (JCCT FRVBUJPO <>
UIF FYUFOU PG TPMWBUJPO MBZFS ćVT UIF BHHSFHBUJPO SFMFBTFT
UIF NPCJMJUZ DPOTUSBJOU PO XBUFS NPMFDVMFT BOE UIFSFGPSF  ಽದ
SFTVMUT JO B GBWPSBCMF JODSFBTF JO UIF FOUSPQZ ಷ (NPM DN− ) = − [ ] 

ਇਉ ಽ PSK ৸
ćF WBMVFT PG əৼ○ NJD BOE əਈ○ NJD BMTP JOEJDBUF UIF NJDFM
MJ[BUJPO PG UIF EZF XJUI DBUJPOJD TVSGBDUBOU UIBU JT $5"# JT XIFSF ದ JT UIF TVSGBDF UFOTJPO JO EZO DN− PS FSHT DN− ਇ =
NPSF GBWPSBCMF BT DPNQBSFE UP /B-4  š  FSHT NPM− ,− BOE ৸ JT UIF DPODFOUSBUJPO PG
TVSGBDUBOU
 4VSGBDF 5FOTJPO BOE 4VSGBDF 1BSBNFUFST ćF TVSGBDF UFO ćF WBMVF PG TVSGBDF FYDFTT DPODFOUSBUJPO ɘ
JO FBDI
TJPO PG TVSGBDUBOU BOE NJYUVSFT PG UIF TVSGBDUBOU BOE EZF XFSF DBTF IBT CFFO DBMDVMBUFE BOE SFQPSUFE JO 5BCMF  *U IBT CFFO
+PVSOBM PG $IFNJTUSZ 

PCTFSWFE GSPN UIF WBMVF UIBU ɘ EFDSFBTFT PO JODSFBTJOH UIF  $PODMVTJPO

EZF DPOUFOU JO UIF NJYUVSF
'SPN UIF TVSGBDF FYDFTT DPODFOUSBUJPO UIF BSFB QFS ćF SFTVMUT JOEJDBUF UIF GPSNBUJPO PG \TVSGBDUBOUEZF^ BHHSF
NPMFDVMF BU UIF TVSGBDFJOUFSGBDF ਐਡ
JO TRVBSF BOHTUSPNT IBT HBUJPO BOE NPSF GBDJMJUBUJPO PG BETPSQUJPO JO DPNQBSJTPO UP
CFFO DBMDVMBUFE VTJOH GPMMPXJOH SFMBUJPO <> NJDFMMJ[BUJPO

"DLOPXMFEHNFOU

ਐਡ =  

ਃɘ ćF BVUIPST UIBOL "MM *OEJB $PVODJM PG 5FDIOJDBM &EVDBUJPO

/FX %FMIJ *OEJB
GPS ĕOBODJBM TVQQPSU UISPVHI B NBKPS
SFTFBSDI QSPKFDU
XIFSF ਃ JT "WPHBESPT OVNCFS
ćF BSFB QFS NPMFDVMF BU UIF JOUFSGBDF ਐਡ
XIJDI QSP
WJEFT JOGPSNBUJPO PG UIF EFHSFF PG QBDLJOH JT GPVOE UP 3FGFSFODFT
JODSFBTF PO JODSFBTJOH EZF DPOUFOU JO UIF NJYUVSF 5BCMF 

<> " , 4BNBOUB BOE 1 "HBSXBM i"QQMJDBUJPO PG OBUVSBM EZFT PO
ćF BOPUIFS QBSBNFUFS XIJDI NFBTVSFT UIF DPODFOUSB UFYUJMFT w *OEJBO +PVSOBM PG 'JCSF  5FYUJMF 3FTFBSDI WPM  OP
UJPO PG TVSGBDUBOU JO UIF MJRVJE QIBTF SFRVJSFE UP QSPEVDF BU  QQ o 
HJWFO BNPVOU PG BETPSQUJPO BU UIF JOUFSGBDF JT UIF OFHBUJWF <> . - (VMSBKBOJ BOE ( %FFQUJ /BUVSBM %ZFT BOE ćFJS "QQMJ
MPHBSJUIN PG UIF DPODFOUSBUJPO PG TVSGBDUBOU JO UIF CVML QIBTF DBUJPOT UP 5FYUJMFT %FQBSUNFOU PG 5FYUJMF 5FDIOPMPHZ *OEJBO
SFRVJSFE UP QSPEVDF B  EZODN SFEVDUJPO JO UIF TVSGBDF *OTUJUVUF PG 5FDIOPMPHZ %FMIJ *OEJBO 
UFOTJPO PG UIF TPMWFOU UIBU JT − PSK ৸ −əದ = 
DBMMFE ਞ৸  <> 1 4 7BOLBS 7 5JXBSJ BOE # (IPSQBEF /BUVSBM %ZFT $POWFO
ćF MBSHFS UIF WBMVF PG ਞ৸ UIF NPSF FďDJFOUMZ JU SFEVDFT UJPO 1SPDFFEJOHT *OEJBO *OTUJUVUF PG 5FDIOPMPHZ %FMIJ *OEJBO
TVSGBDF PS JOUFSGBDJBM UFOTJPO ćF WBMVFT PG ਞ৸ BU EJČFSFOU  FEJUFE CZ % (VQUB BOE . - (VMSBKBOJ
BEEFE EZF DPOUFOUT JO UIF NJYUVSF BSF HJWFO JO 5BCMF  ćF <> 1 4 7BOLBS i$IFNJTUSZ PG OBUVSBM EZFT w 3FTPOBODF WPM  QQ
WBMVF PG ਞ৸ XBT GPVOE UP JODSFBTF PO JODSFBTJOH UIF BNPVOU o 
PG EZF JO UIF NJYUVSF <> 5 #FDIUPME " 5VSDBOV & (BOHMCFSHFS BOE 4 (FJTTMFS
ćF UIFSNPEZOBNJD QBSBNFUFST PG BETPSQUJPO UIBU i/BUVSBM EZFT JO NPEFSO UFYUJMF EZFIPVTFT w +PVSOBM PG $MFBOFS
JT (JCCT GSFF FOFSHZ əৼ○ BE
TUBOEBSE FOUIBMQZ DIBOHF 1SPEVDUJPO WPM  OP  QQ o 
ə৽○ BE
BOE TUBOEBSE FOUSPQZ DIBOHF əਈ○ BE
IBWF BMTP CFFO <> 4 "EFFM 4 "MJ - " #IBUUJ BOE ' ;TJMB i%ZFJOH PG DPUUPO GBCSJD
DBMDVMBUFE CZ VTJOH UIF GPMMPXJOH SFMBUJPO <> VTJOH QPNFHSBOBUF 1VOJDB HSBOBUVN
BRVFPVT FYUSBDU w "TJBO
+PVSOBM PG $IFNJTUSZ WPM  OP  QQ o 
<> 4 /B[ * " #IBUUJB BOE 4 "EFFM i%ZFJOH QSPQFSUJFT PG DPUUPO
əৼ○ BE = − ( ਇਉ) š ਞ৸ −  GBCSJD VTJOH VOJSSBEJBUFE BOE HBNNB JSSBEJBUFE FYUSBDUT PG

&VDBMZQUVT DBNBMEVMFOTJT CBSL QPXEFS w *OEJBO +PVSOBM PG 'JCSF
š  š ਐਡ −  ਇਉ PSK ಼  5FYUJMF 3FTFBSDI WPM  OP  QQ o 
ਓ(əৼ○ BE ) <> 4 (PLUVSL BOE . 5VODBZ i%ZFTVSGBDUBOU JOUFSBDUJPO JO UIF
əਈ○ BE =  
QSFNJDFMMBS SFHJPO w +PVSOBM PG 4VSGBDUBOUT BOE %FUFSHFOUT WPM
ਓਢ  OP  QQ o 
əৼ○ BE = ə৽○ BE − ਉəਈ○ BE  
<> . "MJ "XBO BOE 4 4 4IBI i)ZESPQIPCJD JOUFSBDUJPO PG BN
QIJQIJMJD IFNJDZBOJOF EZFT XJUI DBUJPOJD BOE BOJPOJD TVSGBDUBOU
NJDFMMFT w $PMMPJET BOE 4VSGBDFT " WPM  OP o QQ o
XIFSF ಼ ਇ BOE ਉ BSF UIF TBNF BT EFĕOFE JO 
 
"T UIF WBMVFT PG əৼ○ BE BSF OFHBUJWF JOEJDBUJOH UIBU UIF <> . 4BSLBS BOE 4 1PEEBS i4QFDUSBM TUVEJFT PG NFUIZM WJPMFU
BETPSQUJPO JT TQPOUBOFPVT QSPDFTT JU JT BMTP PCTFSWFE UIBU UIF JO BRVFPVT TPMVUJPOT PG EJČFSFOU TVSGBDUBOUT JO TVQFSNJDFMMBS
BETPSQUJPO CFDPNFT NPSF GBWPSBCMF BU IJHI EZF DPOUFOU ćF DPODFOUSBUJPO SFHJPO w 4QFDUSPDIJNJDB "DUB‰1BSU " WPM  OP
OFHBUJWF WBMVFT PG əৼ○BE BSF NBJOMZ EVF UP UIF MBSHF QPTJUJWF  QQ o 
WBMVFT PG əਈ○ BE BOE FOUSPQZ DIBOHF JT B ESJWJOH GPSDF BT <> . ( /FVNBOO BOE . ) (FIMFO ićF JOUFSBDUJPO PG DBUJPOJD
EJTDVTTFE JO NJDFMMJ[BUJPO EZFT XJUI BOJPOJD TVSGBDUBOUT JO UIF QSFNJDFMMBS SFHJPO w +PVSOBM
PG $PMMPJE "OE *OUFSGBDF 4DJFODF WPM  OP  QQ o
" DPOWFOJFOU XBZ PG NFBTVSJOH UIF SFMBUJWF FČFDUT PG

TPNF TUSVDUVSBM GBDUPS PO NJDFMMJ[BUJPO BOE PS BETPSQUJPO
<> . "CF . 0ITBUP BOE , 0HJOP i*OUFSBDUJPO CFUXFFO BOJPOJD
JT UP EFUFSNJOF JUT FČFDU PO $.$৸ SBUJP XIFSF ৸ JT
TVSGBDUBOUT BOE PJM EZF JO UIF BRVFPVT TPMVUJPOT w $PMMPJE 
UIF DPODFOUSBUJPO PG UIF TVSGBDUBOU JO CVML QIBTF SFRVJSFE UP 1PMZNFS 4DJFODF WPM  OP  QQ o 
QSPEVDF B  EZO DN− SFEVDUJPO JO UIF TVSGBDF UFOTJPO PG UIF <> - (BSDÓB3ÓP 1 )FSWFMMB + $ .FKVUP BOE . 1BSBKØ i4QFD
TPMWFOU
 USPTDPQJD BOE LJOFUJD JOWFTUJHBUJPO PG UIF JOUFSBDUJPO CFUXFFO
"O JODSFBTF JO UIF $.$৸ SBUJP BT B SFTVMU PG UIF DSZTUBM WJPMFU BOE TPEJVN EPEFDZMTVMGBUF w $IFNJDBM 1IZTJDT WPM
JOUSPEVDUJPO PG TPNF GBDUPS JOEJDBUFT UIBU UIF BETPSQUJPO  OP  QQ o 
JT GBDJMJUBUFE NPSF UIBO NJDFMMJ[BUJPO <> ćF WBMVFT PG <> # 4JNPOʊJʊ BOE . ,FSU i" TUVEZ PG BOJPOJD EZFDBUJPOJD
$.$৸ BSF SFQPSUFE JO 5BCMF  *ODSFBTF JO $.$৸ TVSGBDUBOU JOUFSBDUJPOT JO NJYUVSFT PG DBUJPOJD BOE OPOJPOJD
WBMVF PO BEEJUJPO PG EZF DPOUFOU JOEJDBUFT UIF GBDJMJUBUJPO PG TVSGBDUBOUT w %ZFT BOE 1JHNFOUT WPM  OP  QQ o
BETPSQUJPO 
 +PVSOBM PG $IFNJTUSZ

<> 4 "DIBSZB BOE # 3FCFSZ i'MVPSFTDFODF TQFDUSPNFUSJD TUVEZ

PG FPTJO ZFMMPX EZFTVSGBDUBOU JOUFSBDUJPOT w "SBCJBO +PVSOBM PG
$IFNJTUSZ WPM  OP  QQ o 
<> 4 $IBOESBWBOTIJ BOE 4 , 6QBEIZBZ i/BUVSBM EZFTVSGBDUBOU
*OUFSBDUJPO UIFSNPEZOBNJD BOE TVSGBDF QBSBNFUFST w $PM
PSBUJPO 5FDIOPMPHZ WPM  OP  QQ o 
<> " ½OBM i&YUSBDUJPO PG EZFTUVČ GSPN POJPO "MMJVN DFQB -

BOE JUT BQQMJDBUJPO JO UIF EZFJOH PG XPPM GFBUIFSFEMFBUIFS BOE

DPUUPO w 5VSLJTI +PVSOBM PG $IFNJTUSZ WPM  OP  QQ o

<> 5 ' 5BESPT 4VSGBDUBOUT JO "HSPDIFNJDBMT WPM  .BSDFM
%FLLFS /FX :PSL /: 64" 
<> , )PMNCFSH # +PIOTPO # ,SPOCFSH BOE # -JOENBO 4VS
GBDUBOUT BOE 1PMZNFST JO "RVFPVT 4PMVUJPOT +PIO 8JMFZ  4POT
/FX :PSL /: 64" 
<> . + 3PTFO 4VSGBDUBOUT BOE *OUFSGBDJBM 1IFOPNFOB +PIO 8JMFZ
 4POT )PCPLFO /+ 64" SE FEJUJPO 
 International Journal of
Journal of
Advances in Analytical Methods Carbohydrate International Journal of The Scientific
Physical Chemistry
Hindawi Publishing Corporation
in Chemistry
Hindawi Publishing Corporation
Chemistry
Hindawi Publishing Corporation
Inorganic Chemistry
Hindawi Publishing Corporation
World Journal
Hindawi Publishing Corporation
http://www.hindawi.com Volume 2013 http://www.hindawi.com Volume 2013 http://www.hindawi.com Volume 2013 http://www.hindawi.com Volume 2013 http://www.hindawi.com Volume 2013

Photoenergy
International Journal of
International Journal of
Analytical Chemistry
Hindawi Publishing Corporation Hindawi Publishing Corporation
http://www.hindawi.com Volume 2013 http://www.hindawi.com Volume 2013

International Journal of
Electrochemistry

Submit your manuscripts at

http://www.hindawi.com

Bioinorganic Chemistry
and Applications
Hindawi Publishing Corporation Hindawi Publishing Corporation
http://www.hindawi.com Volume 2013 http://www.hindawi.com Volume 2013

Journal of
Chemistry

 Chromatography   Journal of International Journal of Journal of

Hindawi Publishing Corporation

Research International
Hindawi Publishing Corporation
Spectroscopy
Hindawi Publishing Corporation
Spectroscopy
Hindawi Publishing Corporation
Catalysts
Hindawi Publishing Corporation
http://www.hindawi.com Volume 2013 http://www.hindawi.com Volume 2013 http://www.hindawi.com Volume 2013 http://www.hindawi.com Volume 2013 http://www.hindawi.com Volume 2013

ISRN
ISRN ISRN ISRN ISRN Analytical
Inorganic Chemistry Organic Chemistry Physical Chemistry Chromatography Chemistry
Hindawi Publishing Corporation Hindawi Publishing Corporation Hindawi Publishing Corporation Hindawi Publishing Corporation Hindawi Publishing Corporation
http://www.hindawi.com Volume 2013 http://www.hindawi.com Volume 2013 http://www.hindawi.com Volume 2013 http://www.hindawi.com Volume 2013 http://www.hindawi.com Volume 2013