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E-papers Servios Editoriais Ltda., 2001.
Todos os direitos reservados E-papers Servios Editoriais Ltda. proibida a reproduo ou transmisso desta
obra, ou parte dela, por qualquer meio, sem a prvia autorizao dos editores.
Impresso no Brasil.

ISBN 85-87922-25-4

Projeto grfico e diagramao


Lvia Krykhtine

Para adquirir esta e outras publicaes, visite o site:


http://www.e-papers.com.br

E-papers Servios Editoriais


Incubadora de Empresas da Coppe/UFRJ
Caixa Postal 68.568
Cidade Universitria Ilha do Fundo
Cep 21.945-970
Rio de Janeiro Brasil
CNPJ 03.484.075/0001-83
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FODVVLILFDomR GH SROtPHURV TXDQWR j IRUPD PROHFXODU IL[DGD SHODV OLJDo}HV
TXtPLFDV1HVWHFDVRDPROpFXODGHSROtPHURHVWiUHSUHVHQWDGDFRPRXPILRTXH
VHDVVHPHOKDjIRUPDGHXPHVSDJXHWH
&RP UHODomR DR SROtPHUR GR WLSR UDPLILFDGR p LPSRUWDQWH GHVWDFDU TXH HVWH
WHUPRQmRVHUHIHUHDSROtPHURVOLQHDUHVFRQWHQGRJUXSRVODWHUDLVTXHID]HPSDUWH
GDHVWUXWXUDGRPRQ{PHUR$SHQDVDTXHOHVSROtPHURVTXHFRQWHQKDPSHORPHQRV
XPD XQLGDGH PRQRPpULFD FRPSOHWD SHQGXUDGD QD FDGHLD SULQFLSDO VmR
GHQRPLQDGRV SROtPHURV UDPLILFDGRV 3RU H[HPSOR R SROL DFULODWR GH EXWLOD  FXMD
HVWUXWXUDpLOXVWUDGDDVHJXLUDSUHVHQWDJUXSRVpVWHUFRPRJUXSRVODWHUDLV(VWHV
JUXSRV ID]HP SDUWH GD HVWUXWXUD GR SUySULR PRQ{PHUR H SRUWDQWR LVVR QmR p
FRQVLGHUDGRUDPLILFDomR

&RP UHODomR DR SROtPHUR UHWLFXODGR RV VHJPHQWRV TXH XQHP GXDV FDGHLDV
SULQFLSDLVVmRGHQRPLQDGRVOLJDo}HVFUX]DGDV2Q~PHURGHOLJDo}HVFUX]DGDVSRGH

 1Ro}HV%iVLFDVGH3ROtPHURV
VHU FRQWURODGR GH PRGR D REWHU SROtPHURV OHYHPHQWH RX DOWDPHQWH UHWLFXODGRV
WDPEpP GHQRPLQDGRV SROtPHURV FRP EDL[D RX DOWD GHQVLGDGH GH OLJDo}HV
FUX]DGDVUHVSHFWLYDPHQWH
4XDGUR&ODVVLILFDomRGHSROtPHURVTXDQWRjIRUPDPROHFXODUIL[DGDSHODVOLJDo}HVTXtPLFDV

'HVLJQDomRGR
$UTXLWHWXUDGDPROpFXOD 'HILQLomR
SROtPHUR
)RUPDGRSHODVOLJDo}HVGRV
/LQHDU PRQ{PHURVHPXP
FRPSULPHQWRFRQWtQXR

$UTXLWHWXUDWLSRSHQWHFRP
5DPLILFDGRWLSR$
UDPLILFDo}HVORQJDV

$UTXLWHWXUDWLSRSHQWHFRP
5DPLILFDGRWLSR%
UDPLILFDo}HVFXUWDV

(VWUXWXUDGHQGUtWLFDQD
TXDODVUDPLILFDo}HV
5DPLILFDGRWLSR&
WDPEpPDSUHVHQWDP
UDPLILFDo}HV

(VWUXWXUDVQDVTXDLVDV
FDGHLDVSROLPpULFDVHVWmR
5HWLFXODGR
OLJDGDVHQWUHVLIRUPDQGR
XPDUHGHRXUHWtFXOR

SClassificao quanto rotao dos tomos da cadeia em torno de


ligaes primrias (conformao)
$V GXDV FRQIRUPDo}HV EiVLFDV TXH XPD PDFURPROpFXOD SRGH DVVXPLU VmR
]LJXH]DJXH H QRYHOR DOHDWyULR 8P H[HPSOR GH FRQIRUPDomR ]LJXH]DJXH SODQDU p
DTXHODDVVXPLGDSHODPROpFXODGHSROLHWLOHQR

&DUDFWHUL]DomRGH3ROtPHURV 
0DLVXPDYH]UHSUHVHQWDQGRXPDPDFURPROpFXODFRPRXPILRGHHVSDJXHWHD
FRQIRUPDomR HP QRYHOR DOHDWyULR DVVXPLGD SRU XPD PDFURPROpFXOD p
UHSUHVHQWDGDSRUXPDOLQKDHPEDUDoDGD

$ FRQIRUPDomR ]LJXH]DJXH p HQFRQWUDGD HP SROtPHURV QR HVWDGR VyOLGR (VWD
FRQIRUPDomR GR WLSR ]LJXH]DJXH SRGH VHU HVWHQGLGD GLVWRUFLGD RX HP KpOLFH
GHSHQGHQGR GD FRQILJXUDomR GD PDFURPROpFXOD (VWHV SROtPHURV DSUHVHQWDP XP
FHUWR JUDX GH RUGHQDomR GDV FDGHLDV LVWR p DSUHVHQWDP XP FHUWR JUDX GH
FULVWDOLQLGDGH
$ FRQIRUPDomR HP QRYHOR DOHDWyULR SRGH VHU HQFRQWUDGD QR HVWDGR VyOLGR
TXDQGR DV FDGHLDV DSUHVHQWDPVH QR HVWDGR DPRUIR  H p WDPEpP HQFRQWUDGD QR
HVWDGRIXQGLGRHHPVROXomR

 1Ro}HV%iVLFDVGH3ROtPHURV
SClassificao quanto ao encadeamento das unidades monomricas
&RQVLGHUDQGR D SROLPHUL]DomR GH PRQ{PHURV YLQtOLFRV VXEVWLWXtGRV LVWR p
PRQ{PHURVTXHDSUHVHQWDPVXEVWLWXLQWHVRPHQWHHPXPGRViWRPRVGHFDUERQR
GD GXSOD OLJDomR WUrV PRGRV GLVWLQWRV GH HQFDGHDPHQWR GDV XQLGDGHV
PRQRPpULFDVVmRSRVVtYHLVFRPRPRVWUDR4XDGUR
$GHQRPLQDomRFDEHoDpGDGDjSDUWHGDXQLGDGHPRQRPpULFDTXHFRPSRUWDR
JUXSRVXEVWLWXLQWH3RURXWURODGRDGHQRPLQDomRFDXGDpGDGDjSDUWHGDXQLGDGH
PRQRPpULFDTXHQmRSRVVXLJUXSRVXEVWLWXLQWH
4XDGUR7LSRVGHHQFDGHDPHQWRGDVXQLGDGHVPRQRPpULFDV

7LSRGHHQFDGHDPHQWR (VWUXWXUD

&DEHoDFDXGD

&DEHoDFDEHoD
FDXGDFDXGD

0LVWR

2HQFDGHDPHQWRGRWLSRFDEHoDFDXGDGXUDQWHDSROLPHUL]DomRpRPDLVXVXDO
GHYLGR DRV SRVVtYHLV HIHLWRV GH LPSHGLPHQWR HVSDFLDO FDXVDGR SHORV JUXSRV
VXEVWLWXLQWHV

SClassificao quanto ao arranjo dos tomos


3DUWLQGRGHFDGHLDVSROLPpULFDVUHVXOWDQWHVGHHQFDGHDPHQWRGRWLSRFDEHoDFDXGD
FRPR PRVWUDGR QD FODVVLILFDomR GR 4XDGUR   RV JUXSRV VXEVWLWXLQWHV SRGHP
HVWDUGLVSRVWRVQRHVSDoRXQVHPUHODomRDRVRXWURVGHPDQHLUDV FRQILJXUDo}HV 

&DUDFWHUL]DomRGH3ROtPHURV 
GLIHUHQWHV,VWRpSRGHPVHUIRUPDGRVWUrVWLSRVGHDUUDQMRVGLVWLQWRVRVTXDLVVy
SRGHPVHUDOWHUDGRVSHODTXHEUDGHOLJDo}HVTXtPLFDV(VWHVDUUDQMRVUHFHEHUDPR
QRPH GH LVRWiWLFR VLQGLRWiWLFR H DWiWLFR RX KHWHURWiWLFR  VHQGR PRVWUDGRV QR
4XDGUR
4XDGUR&ODVVLILFDomRTXDQWRDRDUUDQMRGRViWRPRV

(VWUXWXUD 'HVLJQDomR 'HILQLomR

7RGRVRVDWRPRVGH
,VRWiWLFR FDUERQRDVVLPpWULFRJH
UDGRVSRVVXHPD
PHVPDFRQILJXUDomR.

$PROpFXODDSUHVHQWD
DOWHUQkQFLDGHFRQIL
6LQGLRWiWLFR JXUDomRGRViWRPRVGH
FDUERQRDVVLPpWULFRV
JHUDGRV

1mRKiRUGHPQD
$WiWLFR VHTrQFLDGH
RX FRQILJXUDomRGRV
KHWHURWiWLFR iWRPRVGHFDUERQRDVVL
PpWULFRVJHUDGRV

SClassificao quanto ao modo de preparao


'XUDQWH R GHVHQYROYLPHQWR GD FLrQFLD GH SROtPHURV GXDV FODVVLILFDo}HV GH
SROtPHURVWrPVLGRXVDGDV8PDFODVVLILFDomRGLYLGHRVSROLPHURVHPSROtPHURVGH
FRQGHQVDomR H SROtPHURV GH DGLomR $ RXWUD GLYLGH RV SROtPHURV HP SROtPHURV GH
HWDSD H SROtPHURV GH FDGHLD 2V WHUPRV FRQGHQVDomR H HWDSDV VmR XVDGRV
QRUPDOPHQWH FRPR VLQ{QLPRV DVVLP FRPR RV WHUPRV DGLomR H FDGHLD 3RUpP DV
GXDVFODVVLILFDo}HVVXUJHPGHGXDVEDVHVGLIHUHQWHVGHFODVVLILFDomRHRXVRGHVWHV
WHUPRV FRPR VLQ{QLPRV SRGH DOJXPDV YH]HV FDXVDU FRQIXVmR $ FODVVLILFDomR
FRQGHQVDomRDGLomR p SULPDULDPHQWH DSOLFiYHO j FRPSRVLomR RX HVWUXWXUD GRV
SROtPHURV $ FODVVLILFDomR HWDSDFDGHLD p EDVHDGD QR 0HFDQLVPR GDV UHDo}HV GH
SROLPHUL]DomR

 1Ro}HV%iVLFDVGH3ROtPHURV
SClassificao condensao-adio (segundo W. H. Carothers)
3ROtPHURV GH FRQGHQVDomR HUDP DTXHOHV SROtPHURV IRUPDGRV D SDUWLU GH
PRQ{PHURV SROLIXQFLRQDLV SRU PHLR GH YiULDV UHDo}HV GH TXtPLFD RUJkQLFD
HQYROYHQGRJUXSRVIXQFLRQDLVFRPDHOLPLQDomRGHDOJXPDPROpFXODSHTXHQD3RU
H[HPSORDUHDomRGHGLDPLQDVHGLiFLGRVIRUPDQGRSROLDPLGDVHHOLPLQDQGRiJXD
GHDFRUGRFRPDHTXDomRDVHJXLU

RQGH5H5VmRJUXSRVDOLIiWLFRVRXDURPiWLFRV$XQLGDGHTXHVHHQFRQWUDHQWUH
SDUrQWHVHVQDIyUPXODGDSROLDPLGDUHSHWHVHGLYHUVDVYH]HVQDFDGHLDSROLPpULFD
H p GHQRPLQDGD XQLGDGH UHSHWLWLYD RX XQLGDGH EiVLFD $ FRPSRVLomR GD XQLGDGH
UHSHWLWLYD GLIHUH GD FRPSRVLomR GRV GRLV PRQ{PHURV SHOD SHUGD GD PROpFXOD GH
iJXD 2V SROtPHURV GH FRQGHQVDomR PDLV FRPXQV H D UHDomR DWUDYpV GDTXDOHOHV
VmRIRUPDGRVVmRPRVWUDGRVQR4XDGUR
4XDGUR3ROtPHURVGHFRQGHQVDomRWtSLFRV

7LSRGH /LJDomR
(VWUXWXUDGRSROtPHURUHVXOWDQWH
SROtPHUR FDUDFWHUtVWLFD
 H2N-R-N2H + HO2 C-R-CO2H
 H-(NH-R- HCO-R-CO-)nOH + H2O
3ROLDPLGD H2N-R-N2H + ClOC-R-COCl
H-(NH-R- HCO-R-CO-)n Cl + HCl
H2N-R-CO2H H-(NH-R-CO-)nOH + H2O
3URWHtQDOm Polmeros de polipeptdeos que ocorrem naturalmente
VHGD H-(NH-R-CONH-R-CO-)nOH + H2O
H2N-R-CO2H + H2N-R-CO2H
 HO-R-OH + HO2 C-R-CO2H
 H-(O-R-OCO-R-CO-)nOH + H2O
3ROLpVWHU HO-R-OH + RO2C-R-CO2R
H-(O-R-OCO-R-CO-)n Cl + ROH
HO-R-CO2H H-(O-R-CO-)nOH + H2O
&HOXORVH Ocorre naturalmente
OC -(C6H12O4-)n - + H2O C6H12O6

&DUDFWHUL]DomRGH3ROtPHURV 
3ROtPHURV GH DGLomR HUDP FODVVLILFDGRV FRPR DTXHOHV IRUPDGRV D SDUWLU GH
PRQ{PHURVVHPRFRUUHUDSHUGDGHXPDPROpFXODSHTXHQD$XQLGDGHUHSHWLWLYD
GHXPSROtPHURGHDGLomRWHPDFRPSRVLomRLJXDOjGRPRQ{PHUR2VSULQFLSDLV
PRQ{PHURV GH DGLomR VmR DTXHOHV RULXQGRV GH PRQ{PHURV YLQtOLFRV (VWHV
PRQ{PHURV VmR LQGX]LGRV D UHDJLU FRP HOHV PHVPRV SDUD IRUPDU SROtPHURV
DWUDYpVGDFRQYHUVmRGHVXDVOLJDo}HVGXSODVHPOLJDo}HVVDWXUDGDVGHDFRUGRFRP
DHTXDomRDVHJXLU
n CH2 = CHR -(CH2 CHR)n-
RQGH5SRGHVHUTXDOTXHUJUXSRVXEVWLWXLQWHWDLVFRPRKLGURJrQLRDOTXLODDULOD
QLWULODpVWHUiFLGRFHWRQDpWHUHKDORJrQLR2VSROtPHURVGHDGLomRPDLVFRPXQV
H RV PRQ{PHURV D SDUWLU GRV TXDLV HOHV VmR SURGX]LGRV VmR PRVWUDGRV QR
4XDGUR
4XDGUR3ROtPHURVGHDGLomRWtSLFRV
3ROtPHUR 0RQ{PHUR 8QLGDGHUHSHWLWLYD
3ROLHWLOHQR

3ROLLVREXWLOHQR

3ROLDFULORQLWULOD

3ROL FORUHWRGHYLQLOD 

3ROLHVWLUHQR

3ROL PHWDFULODWRGH
PHWLOD 

3ROLLVRSUHQR

 1Ro}HV%iVLFDVGH3ROtPHURV
&RPRGHVHQYROYLPHQWRGDFLrQFLDGHSROtPHURVHRHVWXGRGHQRYRVSURFHVVRV
GH SROLPHUL]DomR H REWHQomR GH QRYRV PDWHULDLV D FODVVLILFDomR RULJLQDO GH
&DURWKHUVWRUQRXVHLQDGHTXDGDHPFHUWRVFDVRV3RUH[HPSORRVSROLXUHWDQRVVmR
IRUPDGRV SHOD UHDomR GH GLyLV FRP LVRFLDQDWRV VHP TXH RFRUUD D HOLPLQDomR GH
TXDOTXHUPROpFXODSHTXHQDGHDFRUGRFRPDHTXDomRDVHJXLU

8VDQGR D FODVVLILFDomR RULJLQDO GH &DURWKHUV RV SROLXUHWDQRV VHULDP


FODVVLILFDGRV FRPR SROtPHURV GH DGLomR XPD YH] TXH D XQLGDGH UHSHWLWLYD GR
SROtPHUR WHP D PHVPD FRPSRVLomR TXH DTXHOD GRV PRQ{PHURV (QWUHWDQWR RV
SROLXUHWDQRV VmR HVWUXWXUDOPHQWH PXLWR PDLV VLPLODUHV DRV SROtPHURV GH
FRQGHQVDomRGRTXHDRVSROtPHURVGHDGLomR
3DUD HYLWDU D FODVVLILFDomR LQFRUUHWD GRV SROLXUHWDQRV H GH DOJXQV RXWURV
SROtPHURV DWXDOPHQWH D FODVVLILFDomR WHP FRQVLGHUDGR D HVWUXWXUD TXtPLFD GRV
JUXSRV SUHVHQWHV QDV FDGHLDV SROLPpULFDV 3ROtPHURV GH FRQGHQVDomR WrP VLGR
GHILQLGRVFRPRDTXHOHVFXMDVXQLGDGHVUHSHWLWLYDVVmROLJDGDVHQWUHVLSRUXQLGDGHV
IXQFLRQDLVGLVWLQWDVSRUH[HPSORpVWHUDPLGDXUHWDQRpWHU
(PUHVXPRXPSROtPHURpFODVVLILFDGRFRPRXPSROtPHURGHFRQGHQVDomRVH
SVXDVtQWHVHHQYROYHDHOLPLQDomRGHPROpFXODVSHTXHQDVRX
SRSROtPHURFRQWpPJUXSRVIXQFLRQDLVFRPRSDUWHGDFDGHLDSROLPpULFDHQmR
FRPRJUXSRVSHQGHQWHV

6HRSROtPHURQmRSUHHQFKHQHQKXPGHVVHVUHTXLVLWRVHOHpFODVVLILFDGRFRPR
SROtPHURGHDGLomR

Classificao etapa-cadeia (segundo J. P. Flory)


(VVD FODVVLILFDomR p EDVHDGD QR PHFDQLVPR SHOR TXDO RV SROtPHURV VmR IRUPDGRV
(QWmR SROtPHURV HP HWDSD VmR DTXHOHV SURGX]LGRV SRU PHLR GH UHDomR GH
SROLPHUL]DomRHPHWDSDVHSROtPHURVHPFDGHLDVmRDTXHOHVSURGX]LGRVSRUUHDomR
GHSROLPHUL]DomRHPFDGHLD
1DSROLPHUL]DomRHPHWDSDVRWDPDQKRGDVPROpFXODVGHSROtPHURDXPHQWDD
XPDYHORFLGDGHUHODWLYDPHQWHEDL[D$SDUWLUGRPRQ{PHURIRUPDVHRGtPHURTXH
UHDJLQGR FRP  RXWUR PRQ{PHUR SURGX] R WUtPHUR RX OLJDQGRVH D RXWUR GtPHUR
SURGX] XP WHWUkPHUR H DVVLP SRU GLDQWH DWp D PROpFXOD GR SROtPHUR FRQWHU XP
JUDQGHQ~PHURGHPROpFXODVGRVPRQ{PHURV

&DUDFWHUL]DomRGH3ROtPHURV 
1DSROLPHUL]DomRHPFDGHLDRWDPDQKRILQDOGDVFDGHLDVSROLPpULFDVpDWLQJLGR
TXDVH TXH LPHGLDWDPHQWH DSyV R LQtFLR GD UHDomR $ SROLPHUL]DomR HP FDGHLD
UHTXHUXPLQLFLDGRUDSDUWLUGRTXDOpSURGX]LGDXPDHVSpFLHFRQWHQGRXPFHQWUR
UHDWLYR5 2FHQWURUHDWLYRSRGHVHUXPUDGLFDOOLYUHXPFiWLRQRXXPkQLRQ$
SROLPHUL]DomRRFRUUHFRPDSURSDJDomRGDVHVSpFLHVUHDWLYDVSRUPHLRGHDGLo}HV
VXFHVVLYDV GH PROpFXODV GH PRQ{PHUR 2 FUHVFLPHQWR GD FDGHLD SROLPpULFD p
LQWHUURPSLGRTXDQGRRFHQWURUHDWLYRpGHVWUXtGR
$ )LJXUD  LOXVWUD R PHFDQLVPR GDV UHDo}HV HP HWDSDV H HP FDGHLD 2V
SRQWLQKRVUHSUHVHQWDPPRQ{PHURVQRPHLRUHDFLRQDO

)LJXUD5HSUHVHQWDomRHVTXHPiWLFDGHUHDo}HVGHSROLPHUL]DomR , HPHWDSDV ,, HPFDGHLD

$ FODVVLILFDomR GH SROtPHURV GH DFRUGR FRP R PHFDQLVPR GH SROLPHUL]DomR


DVVLP FRPR DTXHOH EDVHDGR QD FRPSRVLomR H HVWUXWXUD QmR p GH WRGR VHP
DPELJLGDGHV$VSROLPHUL]Do}HVSRUDEHUWXUDGHDQHOGHPRQ{PHURVFtFOLFRVWDLV
FRPRSROL y[LGRGHSURSLOHQR 








 1Ro}HV%iVLFDVGH3ROtPHURV
RXFDSURODFWDPD

SRGHP SURFHGHU WDQWR SHOR PHFDQLVPR HP FDGHLD TXDQWR SHOR PHFDQLVPR HP
HWDSDV GHSHQGHQGR GDV FRQGLo}HV UHDFLRQDLV H GR LQLFLDGRU HPSUHJDGR 2
SROtPHUR REWLGR p R PHVPR LQGHSHQGHQWH GR PHFDQLVPR XWLOL]DGR 7DLV
SROLPHUL]Do}HVHYLGHQFLDPPXLWRFODUDPHQWHDQHFHVVLGDGHGHGLVWLQJXLUVHHQWUHD
FODVVLILFDomR EDVHDGD QR PHFDQLVPR GH SROLPHUL]DomR H DTXHOD EDVHDGD QD
HVWUXWXUDGRSROtPHUR

SClassificao quanto ao comportamento mecnico


([LVWH XPD DPSOD YDULHGDGH GH SROtPHURV VLQWpWLFRV DEUDQJHQGR XPD ODUJD IDL[D
GHSURSULHGDGHV(VWHVSROtPHURVSRGHPVHUDJUXSDGRVHPWUrVFODVVHVSULQFLSDLV
TXDQWRDRFRPSRUWDPHQWRPHFkQLFRTXHVmR
SSOiVWLFRV
SILEUDV
SHODVW{PHURV

$SHVDU GH QmR H[LVWLU XPD GLYLVmR PXLWR EHP OLPLWDGD HQWUH RV JUXSRV HVWD
FODVVLILFDomRp~WLOGRSRQWRGHYLVWDWHFQROyJLFR8PPpWRGRTXHSRGHVHUXVDGR
SDUD GHILQLU XP PHPEUR GH XPD GHVVDV FDWHJRULDV p D DQiOLVH GH XP JUiILFR GH
WHQVmRYHUVXVGHIRUPDomR3OiVWLFRVUtJLGRVHILEUDVVmRUHVLVWHQWHVjGHIRUPDomRH
VmR FDUDFWHUL]DGRV SRU XP YDORU GH PyGXOR DOWR H SRUFHQWDJHQV GH DORQJDPHQWR
EDL[DV (ODVW{PHURV SURGX]HP GHIRUPDomR LPHGLDWD H H[LEHP SRUFHQWDJHQV GH
DORQJDPHQWR DOWDV H UHYHUVtYHLV TXDQGR VXEPHWLGRV D SHTXHQDV WHQV}HV LVWR p
H[LEHP HODVWLFLGDGH 3OiVWLFRV IOH[tYHLV WrP XP FRPSRUWDPHQWR LQWHUPHGLiULR $
)LJXUDGHVFUHYHRFRPSRUWDPHQWRPHFkQLFRGDVWUrVFDWHJRULDV
'H XP PRGR JHUDO RV WHUPRV GHILQLGRV D SDUWLU GR FRPSRUWDPHQWR PHFkQLFR
VmRGHVFULWRVDVHJXLU
S%RUUDFKDV RX HODVW{PHURV VmR PDWHULDLV PDFURPROHFXODUHV TXH H[LEHP
HODVWLFLGDGHHPORQJDIDL[DjWHPSHUDWXUDDPELHQWH
S3OiVWLFRVVmRPDWHULDLVTXHFRQWrPFRPRFRPSRQHQWHSULQFLSDOXPSROtPHUR
RUJkQLFR VLQWpWLFR H VH FDUDFWHUL]DP SHOD FDSDFLGDGH GH VH WRUQDUHP IOXLGRV H
DVVLPVmRFDSD]HVGHVHUHPPROGDGRVSRUDomRGRFDORUHSUHVVmR

&DUDFWHUL]DomRGH3ROtPHURV 
S)LEUD p XP FRUSR TXH WHP XPD UD]mR HOHYDGD HQWUH R FRPSULPHQWR H DV
GLPHQV}HV ODWHUDLV H p FRPSRVWR SULQFLSDOPHQWH GH PDFURPROpFXODV OLQHDUHV
RULHQWDGDVORQJLWXGLQDOPHQWH



)LJXUD&XUYDVGHWHQVmRYHUVXVGHIRUPDomR YV WtSLFDVSDUDXPSOiVWLFRUtJLGRXPDILEUDXP
SOiVWLFRIOH[tYHOHXPHODVW{PHUR

SClassificao quanto s caractersticas de fusibilidade


4XDQWR jV FDUDFWHUtVWLFDV GH IXVLELOLGDGH RV PDWHULDLV SROLPpULFRV SRGHP VHU
GLYLGLGRV HP WHUPRSOiVWLFRV H WHUPRUUtJLGRV 6mR GHQRPLQDGRV WHUPRSOiVWLFRV RV
SROtPHURVFDSD]HVGHVHUHPPROGDGRVYiULDVYH]HVGHYLGRjVXDFDUDFWHUtVWLFDGH
WRUQDUVH IOXLGR VRE D DomR GD WHPSHUDWXUD H GHSRLV UHWRUQDU jV FDUDFWHUtVWLFDV
DQWHULRUHVTXDQGRKiXPGHFUpVFLPRGHWHPSHUDWXUD3RURXWURODGRRVSROtPHURV
TXH QmR VmR FDSD]HV GH WRUQDUHPVH IOXLGRV SRUTXH DV FDGHLDV PDFURPROHFXODUHV
HVWmR XQLGDV HQWUH VL SRU OLJDo}HV TXtPLFDV UHWLFXODomR  VmR GHQRPLQDGRV
WHUPRUUtJLGRV

 1Ro}HV%iVLFDVGH3ROtPHURV
SClassificao quanto estrutura qumica
$ FODVVLILFDomR TXDQWR j HVWUXWXUD TXtPLFD p PHOKRU DSOLFDGD D SROtPHURV GH
FRQGHQVDomR 2 SROtPHUR UHVXOWDQWH p GHVLJQDGR SHOR QRPH GD IDPtOLD TXtPLFD D
TXH SHUWHQFH 3RU H[HPSOR QR FDVR GD SROLPHUL]DomR GR iFLGR WHUHIWiOLFR FRP R
JOLFROHWLOrQLFRRSROtPHURUHVXOWDQWHpRWHUHIWDODWRGHHWLOHQR$UHDomRGRiFLGR
WHUHIWiOLFR FRP JOLFRO EXWLOrQLFR UHVXOWD QR WHUHIWDODWR GH EXWLOHQR (P DPERV RV
FDVRVDHVWUXWXUDTXtPLFDJHUDOGHVVHVSROtPHURVSRGHVHUUHSUHVHQWDGDSRU

3ROtPHURVFRPHVWDHVWUXWXUDJHUDOVmRGHQRPLQDGRVSROLpVWHUHV
'D PHVPD IRUPD SROtPHURV REWLGRV D SDUWLU GH UHDo}HV HQWUH JUXSDPHQWRV
IXQFLRQDLV GDQGR RULJHP D OLJDo}HV DPLGD QD FDGHLD SULQFLSDO VmR GHQRPLQDGRV
SROLDPLGDV

SClassificao quanto variedade de meros que compem a cadeia


$UHDomRGHSROLPHUL]DomRGHHWLOHQRGiRULJHPDRSROLHWLOHQR-iDSROLPHUL]DomR
GR PHWDFULODWR GH PHWLOD Gi RULJHP DR SROL PHWDFULODWR GH PHWLOD  (VVHV VmR
H[HPSORV GH SROtPHURV IRUPDGRV SRU XP ~QLFR WLSR GH PHUR RX XQLGDGH
UHSHWLWLYDHSRULVVRVmRGHQRPLQDGRVKRPRSROtPHURV
8PD FDGHLD GH SROtPHUR SRGH VHU IRUPDGD SRU PDLV GH XP WLSR GH PHUR SRU
H[HPSORXPDFDGHLDFRQVWLWXtGDGHHWLOHQRHSURSLOHQR1HVWHFDVRRSROtPHURp
GHQRPLQDGR FRSROtPHUR RV PRQ{PHURV TXH UHDJLUDP SDUD IRUPDU HVVH
FRSROtPHURV VmR GHQRPLQDGRV FRPRQ{PHURV H D UHDomR TXH GHX RULJHP DR
FRSROtPHUR p GHVLJQDGD FRSROLPHUL]DomR 1RWH TXH p DSHQDV XPD TXHVWmR GH
GHQRPLQDo}HV GLIHUHQWHV SDUD R PHVPR FRPSRVWR GHSHQGHQGR GD VLWXDomR R
HWLOHQRUHDJLQGRVR]LQKRSDUDIRUPDUXPKRPRSROtPHURpFKDPDGRGHPRQ{PHUR
Mi R PHVPR HWLOHQR UHDJLQGR FRP R SURSLOHQR SDUD IRUPDU XP FRSROtPHUR p
FKDPDGRGHFRPRQ{PHUR
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GDURULJHPDGRLVKRPRSROtPHURV
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H
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4XDQGR HVVHV PRQ{PHURV $ H % ID]HP SDUWH GD PHVPD FDGHLD SROLPpULFD
SRGHPVHUIRUPDGDVHVWUXWXUDVGLIHUHQWHV'HSHQGHQGRGDGLVSRVLomRGDVXQLGDGHV
TXtPLFDV DR ORQJR GD HVWUXWXUD GD PDFURPROpFXOD RV FRSROtPHURV DSUHVHQWDP
GLIHUHQWHVGHQRPLQDo}HV24XDGURDSUHVHQWDRVGLYHUVRVWLSRVGHFRSROtPHURV
TXH SRGHP VHU IRUPDGRV TXDQGR GRLV FRPRQ{PHURV VmR LQFRUSRUDGRV j PHVPD
FDGHLDPDFURPROHFXODU
([LVWHP WDPEpP FRSROtPHURV IRUPDGRV SRU PDLV GH GRLV WLSRV GH PHURV
GLIHUHQWHV 3RU H[HPSOR VH R FRSROtPHUR p IRUPDGR SRU WUrV WLSRV GH PHURV
GLIHUHQWHVHOHSRGHVHUGHVLJQDGRWHUSROtPHURSRUpPFRSROtPHURFRQWLQXDVHQGR
R WHUPR JHQpULFR XWLOL]DGR SDUD TXDOTXHU HVWUXWXUD FRQVWLWXtGD SRU GRLV RX PDLV
WLSRVGHPHURVGLIHUHQWHV
4XDGUR&RSROtPHURVIRUPDGRVSRUGRLVWLSRVGHPHUR

'HQRPLQDomR
(VWUXWXUDJHQpULFD 'HILQLomR
GRFRSROtPHUR
$GLVWULEXLomRGDVXQLGDGHV
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~A-A-A-B-A-B-B-A-B-A-B-B~ TXtPLFDVQDFDGHLDpHVVHQFLDO
HVWDWtVWLFR
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&RSROtPHUR
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DOWHUQDGR
SHUIHLWDPHQWHUHJXODU
6HTrQFLDGHXPWLSRGHXQLGDGH
&RSROtPHURHP TXtPLFDpVHJXLGDSRUVHTrQFLD
EORFR ~A-A-A-A-A-A-B-B-B-B-B-B~ GHRXWURWLSRGHXQLGDGHTXtPLFD
IRUPDQGREORFRV

%ORFRVGHXPWLSRGHPRQ{PHUR
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JUDIWL]DGRRX
PRQRPHUR
HQ[HUWDGR
2EVRVtQGLFHVQSRGHPVHULJXDLV
RXGLIHUHQWHV

1.3 Nomenclatura de polmeros


3DUDILQDOL]DUHVWDSHTXHQDLQWURGXomRVHUiIHLWDXPDDERUGDJHPUHVXPLGDVREUH
QRPHQFODWXUDGHSROtPHURV

 1Ro}HV%iVLFDVGH3ROtPHURV
([LVWHPTXDWURWLSRVEiVLFRVGHQRPHQFODWXUDGHSROtPHURV
S1RPHQFODWXUD EDVHDGD QR V  PRQ{PHUR V  GH RULJHP SDUD SROtPHURV
IRUPDGRVDSDUWLUGHXP~QLFRWLSRGHPRQ{PHUR
S1RPHQFODWXUD EDVHDGD QD HVWUXWXUD TXtPLFD UHSHWLWLYD GR SROtPHUR SDUD
SROtPHURVIRUPDGRVDSDUWLUGHGRLVRXPDLVWLSRVGHPRQ{PHURV
S1RPHQFODWXUD HVWDEHOHFLGD SHOD ,83$& ,QWHUQDWLRQDO 8QLRQ RI 3XUH DQG
$SSOLHG&KHPLVWU\ 
S1RPHVFRPHUFLDLV

SNomenclatura baseada no(s) monmero(s) de origem, para polmeros


formados a partir de um nico monmero
(VWD QRPHQFODWXUD p D PHQRV DPEtJXD SDUD QRPHDU SROtPHURV GH DGLomR H
SROtPHURVGHFRQGHQVDomRIRUPDGRVDSDUWLUGHXP~QLFRPRQ{PHUR

Para polmeros de adio


1R FDVR GH KRPRSROtPHURV R QRPH GR SROtPHUR p IRUPDGR SHOD SDUWtFXOD SROL
VHJXLGD GR QRPH GR PRQ{PHUR TXH GHX RULJHP DR SROtPHUR 3RU H[HPSOR
SROLHWLOHQR SROLSURSLOHQR SROLDFULORQLWULOD H SROLHVWLUHQR 4XDQGR R QRPH GR
PRQ{PHUR p XP QRPH FRPSRVWR HVWH DSDUHFH HQWUH SDUrQWHVHV 3RU H[HPSOR
SROL PHWDFULODWRGHPHWLOD SROL FORUHWRGHYLQLOD HSROL y[LGRGHHWLOHQR 

Para polmeros de condensao


1HVWHFDVRRQRPHGRSROtPHURWDPEpPpIRUPDGRSHODSDUWtFXODSROLVHJXLGDSHOR
QRPH GR ~QLFR PRQ{PHUR TXH GHX RULJHP DR SROtPHUR 3RU H[HPSOR QD
FRQGHQVDomR GR iFLGR DPLQR OiXULFR SDUD REWHQomR GH XPD SROLDPLGD VHUi
IRUPDGRRSROL iFLGRDPLQROiXULFR 

SNomenclatura baseada na estrutura qumica repetitiva do polmero, para


polmeros formados a partir de dois ou mais tipos de monmeros

Para polmeros de condensao


3ROtPHURV GH FRQGHQVDomR VLQWHWL]DGRV D SDUWLU GH GRLV RX PDLV WLSRV GH
PRQ{PHURVSRUH[HPSORXPGLiFLGRHXPGLiOFRROVmRQRPHDGRVSHODSDUWtFXOD
SROL VHJXLGD SHOR QRPH GD HVWUXWXUD TXtPLFD GD XQLGDGH UHSHWLWLYD 3RU H[HPSOR
QD UHDomR GH FRQGHQVDomR GR iFLGR WHUHIWiOLFR FRP R JOLFRO HWLOrQLFR SDUD GDU
RULJHP D XP SROLpVWHU D XQLGDGH UHSHWLWLYD IRUPDGD p R WHUHIWDODWR GH HWLOHQR H
SRULVVRRQRPHGRSROtPHURUHVXOWDQWHVHUiSROL WHUHIWDODWRGHHWLOHQR 
1RWH TXH HP WRGRV RV FDVRV QRPHV FRPSRVWRV VHPSUH ILJXUDP HQWUH
SDUrQWHVHV

&DUDFWHUL]DomRGH3ROtPHURV 
Copolmeros
1R FDVR JHUDO GH FRSROtPHURV VmRFLWDGRVRVQRPHVGHWRGRVRVPRQ{PHURVTXH
GHUDP RULJHP DR FRSROtPHUR HQWUH SDUrQWHVHV VHSDUDGRV SRU XPD SDUWtFXOD TXH
LGHQWLILFDRWLSRGHFRSROtPHUR
FRSDUDFRSROtPHURDOHDWyULR
DOWSDUDFRSROtPHURDOWHUQDGR
ESDUDFRSROtPHURHPEORFR
JSDUDFRSROtPHURJUDIWL]DGRRXHQ[HUWDGR
3RU H[HPSOR SROL HVWLUHQRFRPHWDFULODWR GH PHWLOD  SROL HWLOHQRDOWPRQy[LGR
GH FDUERQR  SROL PHWDFULODWR GH PHWLODEDOIDPHWLOHVWLUHQR  H SROL PHWDFULODWR GH
PHWLODJy[LGRGHHWLOHQR 
3DUDRVFDVRVGHFRSROtPHURVDOHDWyULRDOWHUQDGRHHPEORFRpFLWDGRSULPHLUR
RFRPRQ{PHURTXHHQFRQWUDVHHPPDLRUTXDQWLGDGHQDFDGHLDSROLPpULFD3DUDR
FDVR GH FRSROtPHUR JUDIWL]DGR p FLWDGRSULPHLUR R FRPRQ{PHUR TXH FRQVWLWXL D
FDGHLDSULQFLSDOGRFRSROtPHUR
4XDQGR D VHTrQFLD GDV XQLGDGHV TXtPLFDV QR FRSROtPHUR p GHVFRQKHFLGD
XWLOL]DVHDSDUWtFXODFR

SNomenclatura estabelecida pela IUPAC


$,83$&SRVVXLXPOLYURGHUHJUDVSDUDQRPHQFODWXUDGHPDFURPROpFXODV'HXPD
IRUPDEDVWDQWHVLPSOLILFDGDSRGHVHUGLWRTXHD,83$&HVWDEHOHFHSDUDGHVLJQDomR
GHSROtPHURVTXHVHMDXVDGDDSDUWtFXODSROLVHJXLGDGRQRPHGDPHQRUXQLGDGH
UHSHWLGD QD FDGHLD $OJXPDV YH]HV D LGHQWLILFDomR GD PHQRU XQLGDGH UHSHWLGD
WRUQDVH XP WUDEDOKR EDVWDQWH FRPSOH[R H TXH QmR VHUi DERUGDGR QHVWD
LQWURGXomR24XDGURDSUHVHQWDDOJXQVH[HPSORVGHQRPHVHVWDEHOHFLGRVSHOD
,83$& FRPSDUDGRV DRV QRPHV FRPXPHQWH XVDGRV EDVHDGRV QD HVWUXWXUD GR
PRQ{PHURHQDHVWUXWXUDTXtPLFDGDXQLGDGHUHSHWLWLYDJHUDGDSHODFRQGHQVDomR
GHGRLVPRQ{PHURVGLIHUHQWHV


 1Ro}HV%iVLFDVGH3ROtPHURV
4XDGUR1RPHQFODWXUDGHDOJXQVSROtPHURVPDLVFRPXQV

1RPH,83$& (VWUXWXUD 1RPHFRPXP

3ROL PHWLOHQR  3ROLHWLOHQR

3ROL SURSLOHQR  3ROLSURSLOHQR

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3ROL R[LHWLOHQR 3ROL WHUHIWDODWRGH


R[LWHUHIWDORtOD  HWLOHQR 

3ROL GLIOXRURPHWLOHQR  3ROL WHWUDIOXRURHWLOHQR 

SNomes comerciais
2VQRPHVFRPHUFLDLVGHYHPVHUHYLWDGRVXPDYH]TXHXPSROtPHURFRQVWLWXtGRGD
PHVPD HVWUXWXUD TXtPLFD SRGH DSUHVHQWDU QRPHV GLIHUHQWHV XWLOL]DGRV SRU
GLIHUHQWHVIDEULFDQWHV$OpPGLVVRDDVVRFLDomRFRPDHVWUXWXUDGRSROtPHURWRUQD
VHGLILFXOWDGD
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QRPHV TXH Mi VmR EDVWDQWH GLIXQGLGRV SRU H[HPSOR RVQ\ORQV 1\ORQ p R QRPH
FRPHUFLDO GDGR D SROLDPLGDV REWLGRV D SDUWLU GH PRQ{PHURV DOLIiWLFRV QmR
UDPLILFDGRV H QmRVXEVWLWXtGRV $ GHQRPLQDomR Q\ORQ YHP VHPSUH DFRPSDQKDGD
GH XP RX GRLV Q~PHURV RV TXDLV HVWmR DVVRFLDGRV DR Q~PHUR GH iWRPRV GH
FDUERQRGR V PRQ{PHUR V GHRULJHP
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Q\ORQ p R QRPH FRPHUFLDO GR SROL KH[DPHWLOHQR VHEDFDPLGD  e SRVVtYHO
SHUFHEHU TXH R SULPHLUR Q~PHUR FLWDGR LQGLFD R Q~PHUR GH JUXSDPHQWRV
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2XWURH[HPSORpRGRQ\ORQFXMRSROtPHURHPTXHVWmRpRSROL iFLGRDPLQR
FDSUyLFR  1HVWH FDVR D SROLDPLGD IRUPDGD IRL RULXQGD GH VRPHQWH XP WLSR GH
PRQ{PHURRTXDOSRVVXLVHLViWRPRVGHFDUERQRHPVXDHVWUXWXUD

&DUDFWHUL]DomRGH3ROtPHURV 
'H XP PRGR VLPSOLILFDGR RV SROtPHURV WDPEpP VmR FLWDGRV SRU VLJODV 2
4XDGURDSUHVHQWDDOJXQVSROtPHURVVHXVQRPHVFRPXQVHDVVLJODVXWLOL]DGDV


4XDGUR1RPHVFRPXQVHVLJODVXWLOL]DGDVSDUDGHQRPLQDUSROtPHURV

1RPHVFRPXQVGHSROtPHURV 6LJODV
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1RWHTXHDVVLJODVVmREDVHDGDVQDQRPHQFODWXUDGRSROtPHURHVFULWDQDOtQJXD
LQJOHVD3RUH[HPSOR3(73ROL (WK\OHQH7HUHSKWDODWH H363ROL6W\UHQH
$R ORQJR GHVWH OLYUR R OHLWRU WDPEpP LUi QRWDU TXH DV VLJODV GDV WpFQLFDV
DQiOLVHVRXLQVWUXPHQWRVWDPEpPVmREDVHDGDVQDQRPHQFODWXUDHVFULWDQDOtQJXD
LQJOHVD3RUH[HPSORDRVPRPHWULDGHSUHVVmRGHYDSRUpPHQFLRQDGDFRPDVLJOD
9329DSRU3UHVVXUH2VPRPHWU\HDFDORULPHWULDGLIHUHQFLDOGHYDUUHGXUDFRPD
VLJOD'6&'LIIHUHQWLDO6FDQQLQJ&DORULPHWU\

 1Ro}HV%iVLFDVGH3ROtPHURV
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7DJHU$3K\VLFDO&KHPLVWU\RI3RO\PHUV0,53XEOLVKHUV0RVFRZ
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&DUDFWHUL]DomRGH3ROtPHURV 
&DStWXOR

Introduo ao
Comportamento de
Solues de Polmeros
2 HVWXGR GR FRPSRUWDPHQWR GH VROXo}HV GH SROtPHURV UHTXHU XPD DERUGDJHP
WHUPRGLQkPLFD TXH DSUHVHQWD DVSHFWRV GLIHUHQFLDGRV GDTXHOHV JHUDOPHQWH
HPSUHJDGRV QR HVWXGR GH VROXo}HV IRUPDGDV DSHQDV SRU FRPSRQHQWHV GH EDL[R
SHVR PROHFXODU $V SHFXOLDULGDGHV REVHUYDGDV QR FRPSRUWDPHQWR GH VROXo}HV
SROLPpULFDVGHYHPVHDRWDPDQKRGHVXDVFDGHLDVTXHpPXLWRPDLRUGRTXHRGH
XPD PROpFXOD SHTXHQD 2 WDPDQKR H D FRQIRUPDomR GDV PDFURPROpFXODV
LQWURGX]HP DOWHUDo}HV QR FRPSRUWDPHQWR WHUPRGLQkPLFR GH VXDV VROXo}HV H R
HVWXGR GHVVDV SHFXOLDULGDGHV SHUPLWH REWHU LQIRUPDo}HV LPSRUWDQWHV VREUH RV
VLVWHPDVIRUPDGRVSRUPDFURPROpFXODV
$ EDVH GR WUDWDPHQWR WHUPRGLQkPLFR p D PHVPD DGRWDGD SDUD PROpFXODV GH
SHTXHQRWDPDQKRPROHFXODU$VVLPWRGRVRVFRQFHLWRVEiVLFRVHVWDEHOHFLGRVSHOD
ItVLFRTXtPLFD SRGHP VHU DSOLFDGRV WDQWR D VROXo}HV IRUPDGDV SRU PROpFXODV
SHTXHQDVTXDQWRSDUDVROXo}HVHPTXHSHORPHQRVXPGRVFRPSRQHQWHVpXPD
PDFURPROpFXOD $ PDLRU GLIHUHQoD HVWi QR IDWR GH DV PDFURPROpFXODV
DSUHVHQWDUHP GHVYLRV PXLWR JUDQGHV GR FRPSRUWDPHQWR LGHDO 2 SUREOHPD p
UHVROYLGR DSOLFDQGRVH WUDWDPHQWRV HVSHFtILFRV jV WHRULDV TXH VmR DGRWDGDV SDUD
GHVFUHYHUVLVWHPDVIRUPDGRVSRUPROpFXODVSHTXHQDV
$ GHVFULomR GRV VLVWHPDV ItVLFRTXtPLFRV p JHUDOPHQWH IHLWD GH IRUPD
SURJUHVVLYD RQGH RV FRQFHLWRV EiVLFRV GD WHUPRGLQkPLFD YmR VHQGRLQWURGX]LGRV
JUDGXDOPHQWH D SDUWLU GH VLVWHPDV VLPSOHV  'HSRLV R QtYHO GH FRPSOH[LGDGH p
DXPHQWDGRSDVVDQGRVHDGHVFUHYHURFRPSRUWDPHQWRGHVLVWHPDVIRUPDGRVSRU
JDVHV SHUIHLWRV 2V FRQFHLWRV GH HQWDOSLD HQHUJLD OLYUH HQWURSLD HTXLOtEULR HWF
YmRVHQGRGHILQLGRVHDSOLFDGRVVHJXLQGRDVOHLVGDWHUPRGLQkPLFD$SDUWLUGHVWH
SRQWRVmRGHILQLGRVRVFRQFHLWRVDVVRFLDGRVjVVROXo}HVLGHDLV

&DUDFWHUL]DomRGH3ROtPHURV 
8PDVROXomRpFDUDFWHUL]DGDSHORVVHJXLQWHVSDUkPHWURVWHUPRGLQkPLFRV
YROXPH9HQHUJLDLQWHUQD8HQWURSLD6HQHUJLDOLYUHGH*LEEV*HQWDOSLD+HWF
1RFDVRGHXPSURFHVVRHPVROXomRFRVWXPDVHGHWHUPLQDUDGLIHUHQoDHQWUHDV
IXQo}HVWHUPRGLQkPLFDVGDVROXomRHDVPHVPDVIXQo}HVGRVFRPSRQHQWHVSXURV
DQWHV GD GLVVROXomR $ YDULDomR GD HQHUJLD OLYUH GH PLVWXUD *P  p SRUWDQWR D
GLIHUHQoDHQWUHDHQHUJLDOLYUHGDVROXomR *VRO HRVRPDWyULRGDVHQHUJLDVOLYUHVGRV
FRPSRQHQWHVGDPLVWXUD *FRPS 

Gm = Gsol - Gcomp (energia livre de mistura) (2.1)

(PXPDVROXomRLGHDODPHGLGDTXDQWLWDWLYDGHXPSDUkPHWURWHUPRGLQkPLFR
GHXPDVROXomR *86HWF SRGHVHUFRQVLGHUDGDFRPRDVRPDGDVUHVSHFWLYDV
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PRODUGHFDGDXPGHOHVQDVROXomR$VVLP
Gsol = x1G10 + x2G20 + x3G30 + ..... (2.2)

RQGH** H*VmRRVYDORUHVGHHQHUJLDOLYUHGH*LEEVPRODUGRVFRPSRQHQWHV
SXURV H x  x  H x  VmR DV IUDo}HV PRODUHV GRV FRPSRQHQWHV QD VROXomR (VWD
UHODomR OLQHDU QmR p YiOLGD SDUD D PDLRULD GRV VLVWHPDV GHYLGR jV GLIHUHQoDV GH
LQWHUDo}HVHQWUHDVPROpFXODVGRVFRPSRQHQWHVGRVLVWHPDHVWXGDGR,VWRVLJQLILFD
TXHDVSURSULHGDGHVGDVVROXo}HVUHDLVQmRVmRDGLWLYDV

Vsol Vcomp ; Hsol Hcomp ; Ssol Scomp , etc


3DUDFDUDFWHUL]DUPHOKRURFRPSRUWDPHQWRWHUPRGLQkPLFRGRVFRPSRQHQWHVGH
XPD VROXomR p QHFHVViULR XWLOL]DU D IXQomR XVDGD SDUD GHVFUHYHU HVVH
FRPSRUWDPHQWRFRPRIXQomRSDUFLDOPRODU$IXQomRSDUFLDOPRODUFRPRRQRPH
Mi GL] HVWi UHODFLRQDGD D XP GHWHUPLQDGR FRPSRQHQWH HP FRQGLo}HV EHP
GHILQLGDV8PH[HPSORpDGHILQLomRGHSRWHQFLDOTXtPLFR

2.1 Potencial Qumico


8PD GDV IXQo}HV PDLV LPSRUWDQWHV TXH FDUDFWHUL]D R FRPSRUWDPHQWR GH FDGD
FRPSRQHQWH QD VROXomR p R SRWHQFLDO TXtPLFR GR FRPSRQHQWH 2 SRWHQFLDO
TXtPLFRSRGHVHUGHILQLGRFRPRDDOWHUDomRLQILQLWHVLPDOGDHQHUJLDOLYUHGH*LEEV
GH XPD VROXomR TXH RFRUUH FRP D DGLomRGH XP Q~PHUR GH PROHV LQILQLWDPHQWH
SHTXHQRGRFRPSRQHQWHHPTXHVWmRFRQVLGHUDQGRDTXHODSRUomRGDVXEVWkQFLDD
WHPSHUDWXUD SUHVVmR H TXDQWLGDGH GH FDGD XP GRV RXWURV FRPSRQHQWHV
FRQVWDQWHV

 ,QWURGXomRDR&RPSRUWDPHQWRGH6ROXo}HVGH3ROtPHURV
G
= (2.3)
ni
i

T , P, n
(i j )
j

QLM Q~PHURGHPROHVGRFRPSRQHQWHLRXM

$ S H 7 FRQVWDQWHV D DGLomR GH XPD TXDQWLGDGH LQILQLWDPHQWH SHTXHQD GR


FRPSRQHQWHLQDVROXomRPXGDDVXDHQWURSLDHQWDOSLDHHQHUJLDOLYUHGH*LEEV
(VWDV PXGDQoDV TXDQGR UHODFLRQDGDV D  PRO GR FRPSRQHQWH DGLFLRQDGR VmR
FKDPDGDV GH HQWDOSLD SDUFLDO PRODU+L HQWURSLD SDUFLDO PRODU6L H HQHUJLD OLYUH
SDUFLDOPRODU*L

H S G 
Hi = n
; S =

; Gi =
n
ni
i

i p ,T , nj p ,T , nj i p ,T , nj

2SRWHQFLDOTXtPLFRSRGHHQWmRVHUFRQVLGHUDGRLJXDOjHQHUJLDOLYUHGH*LEEV
SDUFLDOPRODU

G
G = = (2.5)

ni
i i

p ,T , nj
7RGDV DV UHODo}HV WHUPRGLQkPLFDV FRQKHFLGDV VmR YiOLGDV SDUD DV IXQo}HV
SDUFLDLVPRODUHV$PDLVXWLOL]DGDVHUi
Gi = Hi - TSi (2.6)

i Gi = Hi - TSi (2.7)

4XDOTXHU IXQomR WHUPRGLQkPLFD H[WHQVLYD IXQomR TXH GHSHQGH GD PDVVD GRV
FRPSRQHQWHVGRVLVWHPD SRGHVHUUHSUHVHQWDGDSHODH[SUHVVmR
Z =Z1n1 + Z2n2 + Z3n3 +... (2.8)

RQGH=pXPDIXQomRWHUPRGLQkPLFDH[WHQVLYD YROXPHHQWDOSLDHQWURSLDHWF H


=LpDIXQomRSDUFLDOPRODUFRUUHVSRQGHQWH

&DUDFWHUL]DomRGH3ROtPHURV 
2.2 Soluo ideal e solues reais
2FRPSRUWDPHQWRGHVLVWHPDVIRUPDGRVSRUPDFURPROpFXODVSRGHVHUGHVFULWRGH
IRUPD VLPSOLILFDGD FRPR XP FRQMXQWR IRUPDGR SRU GRLV FRPSRQHQWHV 4XDQGR
XPDSHTXHQDTXDQWLGDGHGHSROtPHUR FRPSRQHQWH pGLVVROYLGDHPXPVROYHQWH
TXDOTXHU FRPSRQHQWH   DV LQWHUDo}HV HQWUH RV FRPSRQHQWHV GHSHQGHP GD
QDWXUH]DGHDPERVRVFRPSRQHQWHV
7UrVVLWXDo}HVSRGHPVHUHQFRQWUDGDV
SDV LQWHUDo}HV HQWUH DV FDGHLDV GR SROtPHUR RX HQWUH DV PROpFXODV GR VROYHQWH
WrP D PHVPD QDWXUH]D GDV LQWHUDo}HVSROtPHURVROYHQWH1mRH[LVWHLQWHUDomR
SUHIHUHQFLDOQRVLVWHPDORJR
solvente-solvente polmero-solvente polmero-polmero
SDVLQWHUDo}HVSROtPHURSROtPHURHVROYHQWHVROYHQWHVmRPDLVHIHWLYDVGRTXH
DVLQWHUDo}HVSROtPHURVROYHQWHORJR
solvente-solvente
> polmero-solvente
polmero-polmero
SDV LQWHUDo}HV SROtPHURVROYHQWH VmR PDLV HIHWLYDV GR TXH DV LQWHUDo}HV
SROtPHURSROtPHURHVROYHQWHVROYHQWH
solvente-solvente
polmero-solvente >
polmero-polmero
1R SULPHLUR FDVR D VROXomR p GLWD VROXomR LGHDO &RPR QmR H[LVWH LQWHUDomR
SUHIHUHQFLDO QR VLVWHPD QmR RFRUUH OLEHUDomR RX FRQVXPR GH FDORU GXUDQWH R
SURFHVVR GH VROXELOL]DomR &RQVHTHQWHPHQWH D YDULDomR GH HQWDOSLD SDUD XPD
VROXomRLGHDOpLJXDOD]HUR
eLPSRUWDQWHOHPEUDUTXHDHQWURSLDpXPDIXQomRUHODFLRQDGDDRQ~PHURGH
DUUDQMRV GDV PROpFXODV HP VROXomR (P XPD VROXomR LGHDO QmR H[LVWH LQWHUDomR
IDYRUHFLGDHSRUWDQWRRDUUDQMRGDVPROpFXODVpDRDFDVR$HQWURSLDGRVLVWHPDp
IXQomRDSHQDVGDIUDomRPRODU
3DUDVROXo}HVLGHDLV Hi = 0 (2.9)

Si Si (ideal) = - R lnxi (2.10)

&RQVHTHQWHPHQWH D PXGDQoD QR SRWHQFLDO TXtPLFR GR FRPSRQHQWH L HP


VROXo}HVLGHDLVVHUiLJXDOD

i = -T Si (ideal) = - RT lnxi   

 ,QWURGXomRDR&RPSRUWDPHQWRGH6ROXo}HVGH3ROtPHURV
RXVHMDVyGHSHQGHGDIUDomRPRODUGRFRPSRQHQWHL x L QDVROXomR
$IUDomRPRODUSDUDVROXo}HVLGHDLVpUHODFLRQDGDjSUHVVmRGHYDSRUSRUPHLR
GHXPDH[SUHVVmRHPStULFDFRQKHFLGDFRPROHLGH5DRXOW (TXDomR 
xi = pi/pio (2.12)

RQGHSLpDSUHVVmRGHYDSRUGRFRPSRQHQWHLQDVROXomRHSLRpDSUHVVmRGHYDSRU
GRFRPSRQHQWHLSXUR
6H R FRPSRUWDPHQWR GD VROXomR QmR VHJXH D OHL GH 5DRXOW D VROXomR p
GHQRPLQDGD VROXomR QmRLGHDO RX VROXomR UHDO e R TXH DFRQWHFH FRP D PDLRU
SDUWHGRVVLVWHPDV
6H D UD]mR SLSLR IRU FRORFDGD HP JUiILFR HP IXQomR GHx L WUrV VLWXDo}HV GLVWLQWDV
SRGHPVHUREVHUYDGDVGHSHQGHQGRGDQDWXUH]DGRVLVWHPD(VWDVVLWXDo}HVHVWmR
LOXVWUDGDVQD)LJXUDRQGHSHSVmRUHVSHFWLYDPHQWHDVSUHVV}HVGHYDSRUGR
VROYHQWHSXURHQDVROXomRH[pDIUDomRPRODUGRSROtPHURQDVROXomR

)LJXUD'HSHQGrQFLDGDSUHVVmRGHYDSRUFRPDFRPSRVLomRGDVROXomR $ VROXomRLGHDO % GHVYLR


QHJDWLYRGDLGHDOLGDGH & GHVYLRSRVLWLYRGDLGHDOLGDGH

$ FXUYD $ H[LEH XPD GHSHQGrQFLD OLQHDU WDO FRPR SUHYr D OHL GH 5DRXOW (VWD
VROXomRSRVVXLXPFRPSRUWDPHQWRLGHDO1mRH[LVWHLQWHUDomRSUHIHUHQFLDOHQWUHRV
FRPSRQHQWHVHQRUPDOPHQWHRFRUUHTXDQGRVXEVWkQFLDVGHHVWUXWXUDTXtPLFDHGH
WDPDQKRVPROHFXODUHVVHPHOKDQWHVVmRPLVWXUDGDV
$FXUYD%DSUHVHQWDXPGHVYLRQHJDWLYRGDOHLGH5DRXOWRXVHMDSLSLR<xL(VWH
FRPSRUWDPHQWRLQGLFDTXHDVLQWHUDo}HVVROXWRVROYHQWHVmRPDLVLPSRUWDQWHVGR

&DUDFWHUL]DomRGH3ROtPHURV 
TXH DV LQWHUDo}HV VROXWRVROXWR RX VROYHQWHVROYHQWH $ ERD LQWHUDomR VROXWR
VROYHQWHGLPLQXLRQ~PHURGHPROpFXODVGRFRPSRQHQWHQDIDVHYDSRU$VVLPD
SUHVVmRGHYDSRUGRVROYHQWHQDVROXomRpPHQRUGRTXHDGRVROYHQWHSXUR
$FXUYD&DSUHVHQWDXPGHVYLRSRVLWLYRGDOHLGH5DRXOWHLQGLFDTXHDLQWHUDomR
VROXWRVROYHQWH p IUDFD $V PROpFXODV WHQGHP D SDVVDU HP PDLRU Q~PHUR SDUD D
IDVHYDSRUDXPHQWDQGRDSUHVVmRGHYDSRU
(PVROXo}HVSROLPpULFDVRSROtPHURQmRFRQVHJXHSDVVDUSDUDRHVWDGRGHYDSRU
GHYLGR DR VHX DOWR SHVR PROHFXODU 3RGHVH FRQVLGHUDU HQWmR TXH D SUHVVmR GH
YDSRUGRSROtPHURpSUDWLFDPHQWH]HUR'HVWDIRUPDRTXHVHPHGHpDSUHVVmRGH
YDSRUGRVROYHQWHQDVROXomReXPH[HPSOROLPLWHGDFXUYD%
2GHVYLRGDLGHDOLGDGHVLJQLILFDTXH

H 0 e H i 0 (2.13)

Smis Smis (ideal) (2.14)

(VVH GHVYLR SRGH VHU GHWHUPLQDGR SHOR FiOFXOR GD YDULDomR GD IXQomR
WHUPRGLQkPLFD HP H[FHVVR TXH p D GLIHUHQoD HQWUH D YDULDomR GD IXQomR
WHUPRGLQkPLFD QD IRUPDomR GH XPD VROXomR UHDO H D YDULDomR GD IXQomR
WHUPRGLQkPLFDQDIRUPDomRGHXPDVROXomRLGHDO$VVLP

Gexc = Gmis - G (ideal) (2.15)

Sexc = Smis - S (ideal) (2.16)

&RPELQDQGRDVHTXDo}HVHREWpPVHDGHILQLomRGRSRWHQFLDOTXtPLFR
SDUDXPDVROXomRUHDOEDVHDGDQDUD]mRHQWUHDVSUHVV}HVGHYDSRUGRVROYHQWHQD
VROXomRHGRVROYHQWHSXURFRPRGHVFULWDDVHJXLU
pi 
i
= G i = RT ln o
(2.17)
pi

SL SUHVVmRGHYDSRUSDUFLDOGRVROYHQWHQDVROXomR
R
SL  SUHVVmRGHYDSRUSDUFLDOGRVROYHQWHSXUR

2.3 Processo de dissoluo de um polmero


8PD VROXomR YHUGDGHLUD SRGH VHU IRUPDGD TXDQGR H[LVWH LQWHUDomR HQWUH RV
FRPSRQHQWHV 2V FRPSRQHQWHV VH GLVSHUVDP HVSRQWkQHDPHQWH HP PROpFXODV
iWRPRVRXtRQVVHPDQHFHVVLGDGHGHWUDEDOKRH[WHUQR6ROXo}HVYHUGDGHLUDVVmR

 ,QWURGXomRDR&RPSRUWDPHQWRGH6ROXo}HVGH3ROtPHURV
FDUDFWHUL]DGDVSHORJUDXGHGLVSHUVmRPROHFXODU2VLVWHPDpKRPRJrQHRRXVHMD
QmRDSUHVHQWDLQWHUIDFH6ROXo}HVYHUGDGHLUDVVmRFDUDFWHUL]DGDVSHODHVWDELOLGDGH
WHUPRGLQkPLFD2VLVWHPDpFRQVWLWXtGRSRUXPD~QLFDIDVH
6ROXo}HV YHUGDGHLUDV GH SROtPHURV SRVVXHP FDUDFWHUtVWLFDV HVSHFtILFDV TXH DV
GLVWLQJXHP GH VROXo}HV GH VXEVWkQFLDV GH EDL[R SHVR PROHFXODU (VWDV
FDUDFWHUtVWLFDVVmRGHYLGDVjJUDQGHGLIHUHQoDGHWDPDQKRPROHFXODUHLQFOXHP
SLQFKDPHQWRDQWHVGDGLVVROXomR
SYLVFRVLGDGHDOWD
SGLIXVmROHQWD
SLQFDSDFLGDGHGHDWUDYHVVDUXPDPHPEUDQDVHPLSHUPHiYHO

2SURFHVVRGHGLVVROXomRRFRUUHGDVHJXLQWHIRUPD
 TXDQGRXPSROtPHURpSRVWRHPFRQWDWRFRPXPVROYHQWHRSULPHLURSURFHVVR
TXHRFRUUHpRLQFKDPHQWRGRSROtPHURRXVHMDRSROtPHURDEVRUYHPROpFXODV
GR VROYHQWH DXPHQWDQGR D PDVVD H R YROXPH 1R ILQDO GR LQFKDPHQWR HOHV
IRUPDPXPD~QLFDFDPDGDTXHFRQVLVWHGRSROtPHURHGROtTXLGRDEVRUYLGR
 R SROtPHUR LQFKDGR FRH[LVWH GXUDQWH DOJXP WHPSR FRP D FDPDGD GR OtTXLGR
SXUR
 DSyVXPFHUWRWHPSRTXDQGRDVFDGHLDVSROLPpULFDVFRQVHJXHPDGTXLULUPDLRU
PRELOLGDGH HODV FRPHoDP D VH GLIXQGLU OHQWDPHQWH QR VROYHQWH DWp IRUPDU
XPDVROXomRKRPRJrQHD

1RLQtFLRGRSURFHVVRH[LVWHSRUWDQWRVROYHQWHSXURHXPDVROXomRFRPSRVWD
GHSROtPHURVROYHQWH2SRWHQFLDOTXtPLFRGRVROYHQWHSXURRpPDLRUGRTXHR
SRWHQFLDO TXtPLFR GR VROYHQWH QD VROXomR  2 HTXLOtEULR WHUPRGLQkPLFR p
DOFDQoDGRTXDQGR  RXVHMD R  3DUDTXHLVWRRFRUUDDVPROpFXODVGR
VROYHQWHYmRSDVVDQGRFDGDYH]PDLVSDUDDVROXomRDXPHQWDQGRGHVWDIRUPDR
SRWHQFLDOTXtPLFRGDVROXomR
2 LQFKDPHQWR QmR p QHFHVVDULDPHQWH XPD SHQHWUDomR GH SHTXHQDV PROpFXODV
QD IDVH GR SROtPHUR HQFKHQGR VHXV HVSDoRV YD]LRV 2 LQFKDPHQWR HQYROYH
LQHYLWDYHOPHQWH XPD PXGDQoD QR DUUDQMR HVSDFLDO GDV FDGHLDV SROLPpULFDV
UHVXOWDQGR HP XP DXPHQWR GH YROXPH GD DPRVWUD 2 LQFKDPHQWR SRGH VHU
LOLPLWDGRRXOLPLWDGR

Inchamento ilimitado
e R LQFKDPHQWR TXH SDVVD HVSRQWDQHDPHQWH SDUD D GLVVROXomR 0ROpFXODV GH
SROtPHUR GLIHUHP HP WDPDQKR H SRUWDQWR WrP PRELOLGDGHV GLIHUHQWHV $V
PROpFXODV GR VROYHQWH SRVVXHP PDLRU PRELOLGDGH GR TXH DV PROpFXODV GR
SROtPHUR 'HVWD IRUPD R SROtPHUR QmR WHP WHPSR GH SDVVDU SDUD D IDVH GR

&DUDFWHUL]DomRGH3ROtPHURV 
VROYHQWH$QWHVGHVHGLVVROYHURSROtPHURDEVRUYHJUDQGHSDUWHGRVROYHQWHLVWR
pLQFKD

Inchamento limitado
4XDQGRDLQWHUDomRGRSROtPHURFRPRVROYHQWHpOLPLWDGDDRHVWiJLRGHVRUomRGR
OtTXLGRSHORSROtPHURDGLVVROXomRHVSRQWkQHDGRSROtPHURQmRRFRUUHRXVHMDDV
FDGHLDV SROLPpULFDV QmR VH VHSDUDP FRPSOHWDPHQWH XPDV GDV RXWUDV 2FRUUH D
IRUPDomRGHGXDVIDVHVDVROXomRGROtTXLGRQRSROtPHURHXPDRXWUDGRVROYHQWH
SXUR RX GH XPD VROXomR EHP GLOXtGD GH SROtPHUR (VWDV IDVHV VH HQFRQWUDP
FODUDPHQWH VHSDUDGDV (VWH SURFHVVR SRGH RFRUUHU WDQWR HP SROtPHURV OLQHDUHV
FRPRHPSROtPHURVUHWLFXODGRV
(P SROtPHURV OLQHDUHV R LQFKDPHQWR p OLPLWDGR VRE GHWHUPLQDGDV FRQGLo}HV
WDLV FRPR WHPSHUDWXUD HFRQFHQWUDomRGDVROXomR4XDQGRDLQWHUDomRSROtPHUR
SROtPHURpPDLRUGRTXHDLQWHUDomRSROtPHURVROYHQWHDVFDGHLDVQmRVHVHSDUDP
FRPSOHWDPHQWH &RP D YDULDomR GD WHPSHUDWXUD R LQFKDPHQWR OLPLWDGR SRGH VH
WRUQDULOLPLWDGRUHVXOWDQGRHPXPDVROXomRKRPRJrQHD
6H R SROtPHUR p FRPSRVWR SRU XPD UHGH WULGLPHQVLRQDO IRUPDGD DWUDYpV GH
OLJDo}HV TXtPLFDV HQWUH DV FDGHLDV SROLPpULFDV HVWDV FDGHLDV QmR VH VHSDUDP HP
TXDOTXHU WHPSHUDWXUD DEDL[R GD GHFRPSRVLomR GR SROtPHUR  (OHV QmR VH
GLVVROYHPHRSURFHVVRGHGLVVROXomRpOLPLWDGRDRHVWiJLRGHLQFKDPHQWR
$ TXDQWLGDGH GH OtTXLGR DEVRUYLGR SRU XQLGDGH GH PDVVD RX YROXPH GR
SROtPHUR p GHQRPLQDGDJUDX GH LQFKDPHQWR 2 JUDX GH LQFKDPHQWR GHSHQGHGD
LQWHUDomRSROtPHURVROYHQWHHGRJUDXGHUHWLFXODomRQDDPRVWUD

2.4 Afinidade termodinmica entre um solvente e um polmero


6RE R DVSHFWR WHUPRGLQkPLFR GXDV RX PDLV VXEVWkQFLDV VmR FDSD]HV GH VH
PLVWXUDUHP VH R SURFHVVR RFRUUHU HVSRQWDQHDPHQWH QD GLUHomR GD IRUPDomR GD
PLVWXUD
3URFHVVRVDSUHVVmRHDWHPSHUDWXUDFRQVWDQWHVRFRUUHPHVSRQWDQHDPHQWHQD
GLUHomR GD GLPLQXLomR GD HQHUJLD OLYUH GH *LEEV RX QD GLUHomR GD GLPLQXLomR GR
SRWHQFLDOTXtPLFRGHFDGDFRPSRQHQWH
*PSURFHVVRHVSRQWkQHR
*P HVWDGRGHHTXLOtEULR
*P!SURFHVVRQmRRFRUUH

4XDQWR PDLRU IRU D GLIHUHQoD HQWUH D HQHUJLD OLYUH GD VROXomR H D GRV
FRPSRQHQWHVPDLRUVHUiDDILQLGDGHWHUPRGLQkPLFDHPDLVSHUIHLWRVHUiRSURFHVVR
GHLQWHUDomR

 ,QWURGXomRDR&RPSRUWDPHQWRGH6ROXo}HVGH3ROtPHURV
(P WHUPRV SUiWLFRV H UHVXPLGRV SRGHVH GL]HU TXH R FRQFHLWR GD DILQLGDGH
WHUPRGLQkPLFD SRGH VHU HVWHQGLGR DRV VROYHQWHV FRQVLGHUDQGR D TXDOLGDGH
WHUPRGLQkPLFDGRVROYHQWH$VVLPRVVROYHQWHVSRGHPVHUFRQVLGHUDGRV
S%RQVVROYHQWHVVROYHQWHVHPTXHRVYDORUHVGH *H LVmRDOWRVTXDQGR
HOHVLQWHUDJHPFRPSROtPHURV
S0DXVVROYHQWHVVROYHQWHVHPTXHDLQWHUDomRFRPSROtPHURVpDFRPSDQKDGD
GHSHTXHQDYDULDomRGH*HL

(QWmR p SUHFLVR FRQKHFHU RV YDORUHV GH * H  L SDUD DYDOLDU D TXDOLGDGH GR
VROYHQWH
$ DILQLGDGH WHUPRGLQkPLFD HQWUH SROtPHUR H VROYHQWH SRGH VHU DYDOLDGD SRU
DOJXPDVWpFQLFDV
S0HGLGDGDSUHVVmRGHYDSRUGRVROYHQWHQDVROXomR
S0HGLGDGDSUHVVmRRVPyWLFD
S0HGLGDGDSUHVVmRGHLQFKDPHQWR
S'HWHUPLQDomRGRVHJXQGRFRHILFLHQWHYLULDO

,VWR TXHU GL]HU TXH D DILQLGDGH WHUPRGLQkPLFD SRGH VHU FDUDFWHUL]DGD SRU
DOJXQV SDUkPHWURV D YDULDomR QR SRWHQFLDO TXtPLFR GRV FRPSRQHQWHV L D
HQHUJLD OLYUH GH PLVWXUD *P R VHJXQGR FRHILFLHQWH YLULDO $ H R SDUkPHWUR GH
LQWHUDomRGH)ORU\+XJJLQV

2.4.1 Presso de vapor na soluo de polmero


1RHVWDGRGHHTXLOtEULRKiVHPSUHYDSRUGRVFRPSRQHQWHVVREUHDVROXomROtTXLGD
8PDPDFURPROpFXODQmRFRQVHJXHSDVVDUSDUDRHVWDGRGHYDSRU/RJRDSUHVVmR
SDUFLDOGRVHXYDSRUpSUDWLFDPHQWHLJXDOD]HUR$SUHVVmRGHYDSRUTXHVHPHGHp
HVVHQFLDOPHQWH D SUHVVmR GH YDSRU GR FRPSRQHQWH GH EDL[R SHVR PROHFXODU
VROYHQWH  VREUH D VROXomR (VWD p VHPSUH PHQRU GR TXH D SUHVVmR GH YDSRU GR
VROYHQWH SXUR 4XDQWR PDLRU IRU D LQWHUDomR SROtPHURVROYHQWH PHQRU VHUi D
SUHVVmRGHYDSRUGRVROYHQWHQDVROXomR

2.4.2 Presso osmtica


2VPRVHpRIHQ{PHQRGHSHQHWUDomRGHXPVROYHQWHHPXPDVROXomRDWUDYpVGH
XPD PHPEUDQD VHPLSHUPHiYHO LVWR p XPD PHPEUDQD SHUPHiYHO VRPHQWH D
PROpFXODVSHTXHQDV3DUDDREVHUYDomRGRIHQ{PHQRDVROXomRGHXPVROXWRHP
XP GHWHUPLQDGR VROYHQWH H R VROYHQWH SXUR HVWmR VHSDUDGRV SHOD PHPEUDQD
VHPLSHUPHiYHO $ WHQGrQFLD GDV PROpFXODV GH VROYHQWH HP SDVVDU HVSRQWD
QHDPHQWH SDUD D VROXomR GHYLGR j GLIHUHQoD GH SRWHQFLDO TXtPLFR     p
HVWLPDGDTXDQWLWDWLYDPHQWHSHODSUHVVmRRVPyWLFD

&DUDFWHUL]DomRGH3ROtPHURV 
2.4.3 Presso de inchamento
6ROXo}HVFRPDOWDFRQFHQWUDomRGHXPSROtPHURVmREDVLFDPHQWHVROXo}HVGHXP
FRPSRQHQWHGHEDL[RSHVRPROHFXODUHPXPSROtPHURRXHPRXWUDVSDODYUDVXP
SROtPHUR LQFKDGR $ H[SHULrQFLD p FRQGX]LGD FRQILQDQGR D DPRVWUD HP XP
FRPSDUWLPHQWRFRPSDUHGHVUtJLGDVFRQWHQGRDSHQDVXPSHTXHQRRULItFLRSDUDD
DGLomR GR VROYHQWH $VVLP R LQFKDPHQWR GR SROtPHUR RFRUUH VHP DXPHQWR GH
YROXPH H D SUHVVmR H[HUFLGD VREUH HVWDV SDUHGHV p GHQRPLQDGD SUHVVmR GH
LQFKDPHQWR
4XDQWR PDLRU IRU D LQWHUDomR SROtPHURVROYHQWH PDLRU VHUi D WHQGrQFLD GR
VROYHQWH GH SDVVDU SDUD D VROXomR VROYHQWH GLVVROYLGR QR SROtPHUR  H PDLRU VHUi
HQWmRDSUHVVmRGHLQFKDPHQWR
$SUHVVmRGHLQFKDPHQWRpXPIHQ{PHQRVHPHOKDQWHDRGDSUHVVmRRVPyWLFD$
SUHVVmRGHLQFKDPHQWRpPHGLGDHPVROXo}HVFRQFHQWUDGDVHDSUHVVmRRVPyWLFDp
GHWHUPLQDGDXVDQGRVROXo}HVGLOXtGDV
(VWD WpFQLFD SHUPLWH DYDOLDU D DILQLGDGH HQWUH VROYHQWH H SROtPHUR TXDQGR VH
HVWXGDPDPRVWUDVGHSROtPHURVUHWLFXODGRV

2.4.4 Determinao do segundo coeficiente virial


2 VHJXQGR FRHILFLHQWH YLULDO $ p REWLGR SRU PHLR GH XP WUDWDPHQWR WHyULFR
QHFHVViULR DR FiOFXOR GH SDUkPHWURV WHUPRGLQkPLFRV REWLGRV D SDUWLU GH GDGRV
H[SHULPHQWDLVGHYDULDomRGHSUHVVmRGHYDSRUSUHVVmRRVPyWLFDRXHVSDOKDPHQWR
GHOX]GHVROXo}HVSROLPpULFDV7DLVWpFQLFDVVHUmRGHWDOKDGDVSRVWHULRUPHQWH
2VHJXQGRFRHILFLHQWHYLULDO$GHSHQGHGHYiULRVIDWRUHVWDLVFRPR
SWHPSHUDWXUD$GHFUHVFHFRPRDXPHQWRGDWHPSHUDWXUD
SVLVWHPDSROtPHURVROYHQWH
SSHVRPROHFXODUHGLVWULEXLomRGRSHVRPROHFXODUGRSROtPHUR
SWDWLFLGDGHGRSROtPHUR

2.5 Fatores que afetam a dissoluo e inchamento dos polmeros


2VSULQFLSDLVIDWRUHVTXHDIHWDPDGLVVROXomRGHXPSROtPHURHPXPVROYHQWHVmR
GHVFULWRVDVHJXLU

2.5.1 Natureza qumica do solvente e do polmero


$ VROXELOLGDGH P~WXD GDV VXEVWkQFLDV GHSHQGH GD VXD FRPSRVLomR TXtPLFD 2
SURFHVVRGHGLVVROXomRpXPDPHGLGDGDVIRUoDVLQWHUPROHFXODUHV
$VVLPFRPRDVPROpFXODVSHTXHQDVDVFDGHLDVSROLPpULFDVSRGHPHVWDUOLJDGDV
HQWUHVLDWUDYpVGHOLJDo}HVSULPiULDVHVHFXQGiULDV
(QWHQGHVHSRUOLJDo}HVSULPiULDVDVOLJDo}HVFRYDOHQWHVH[LVWHQWHVHPFDGHLDV
GH SROtPHURV OLQHDUHV UDPLILFDGRV H UHWLFXODGRV 6mR DV OLJDo}HV SUHGRPLQDQWHV

 ,QWURGXomRDR&RPSRUWDPHQWRGH6ROXo}HVGH3ROtPHURV
TXDQGR VH WUDWD GH SROtPHURV ([LVWHP RXWURV WLSRV GH OLJDomR SULPiULD PHQRV
IUHTHQWHVQRVSROtPHURV6mRDVOLJDo}HVL{QLFDVTXHRFRUUHPHPLRQ{PHURVHDV
OLJDo}HVSRUFRRUGHQDomRIRUPDGDVHPHVWDGRVGHWUDQVLomR
/LJDo}HV VHFXQGiULDV RXIRUoDV LQWHUPROHFXODUHV RXIRUoDV GH YDQ GHU:DDOV
OLJDo}HV KLGURJrQLR LQWHUDomR GLSRORGLSROR HWF  VmR IRUoDV TXH DWXDP HQWUH
PROpFXODVRXHQWUHVHJPHQWRVGHFDGHLDVHFRQWULEXHPGHIRUPDVLJQLILFDWLYDSDUD
DV SURSULHGDGHV GRV SROtPHURV (VWDV OLJDo}HV FDUDFWHUL]DP XPD LQWHUDomR GH
RUGHPLQWUDRXLQWHUPROHFXODURTXHpXPDPHGLGDGRJUDXGHDWUDomRHQWUHDV
PROpFXODV6mRUHFRQKHFLGRVRVWLSRVFLWDGRVDVHJXLU
S)RUoDV GH GLVSHUVmR  IRUoDV GH DWUDomR TXH VXUJHP QDV PROpFXODV GHYLGR jV
IOXWXDo}HVQDFRQILJXUDomRLQVWDQWkQHDGHHOpWURQVHQ~FOHRV1mRH[LVWHGLSROR
HDSRODUL]DomRpUHVXOWDQWHGDPRELOLGDGHGRVHOpWURQVVYH]HVVmRFKDPDGDV
GHIRUoDVGHYDQGHU:DDOVHIRUoDVGHGLVSHUVmRGH/RQGRQ
S)RUoDV GH LQGXomR  IRUoDV LQWHUPROHFXODUHV HQWUH GLSRORV SHUPDQHQWHV H
GLSRORVLQGX]LGRV(VWDVIRUoDVVmRJHUDGDVSRUPROpFXODVSRODUHVTXHHVWDQGR
QDYL]LQKDQoDGHPROpFXODVTXHQmRSRVVXHPGLSRORVSHUPDQHQWHVSURPRYHP
XP OHYH GHVORFDPHQWR GRV HOpWURQV H Q~FOHRV GD PROpFXOD YL]LQKD LQGX]LQGR
XP  PRPHQWR GLSRODU 6mR FRQKHFLGDV FRPR IRUoDV GH 'HE\H VmR IUDFDV H
LQGHSHQGHPGDWHPSHUDWXUD
S)RUoDV GLSRODUHV  RFRUUHP HP PROpFXODV SRODUHV LVWR p PROpFXODV TXH
FRQWpPiWRPRVGLIHUHQWHVFRPFDUJDVHOpWULFDVLJXDLVHRSRVWDVTXHJHUDPXP
PRPHQWR GLSRODU $V IRUoDV GLSRODUHV RX IRUoDV GH .HHVRP GHSHQGHP
IRUWHPHQWHGDWHPSHUDWXUD
S/LJDomRKLGURJrQLRpDPDLVLPSRUWDQWHSRLVRFRUUHHPLQ~PHURVVLVWHPDV
SROLPpULFRV H SULQFLSDOPHQWH QDTXHOHV UHODFLRQDGRV jV SURWHtQDV H RXWURV
ELRSROtPHURV &RQVLGHUDQGR R FRQFHLWR FOiVVLFR GH OLJDomR TXtPLFD HP TXH R
iWRPRGHKLGURJrQLRVyIRUPDXPDOLJDomRFRYDOHQWHDOLJDomRKLGURJrQLRSRGH
VHUFRQVLGHUDGDGHFDUiWHUHOHWURVWiWLFRRXL{QLFR$OLJDomRKLGURJrQLRRFRUUH
HQWUH GRLV JUXSRV IXQFLRQDLV GH XPD ~QLFD PROpFXOD RX HQWUH PROpFXODV
GLIHUHQWHV(PXPGRVJUXSRVRiWRPRGHKLGURJrQLRHVWiJHUDOPHQWHOLJDGRD
XPJUXSRDFtGLFR GRDGRUGHSUyWRQV LVWRpKLGUR[LODFDUER[LODDPLQDHWF2
RXWUR JUXSR WHP TXH VHU EiVLFR DFHSWRU GH SUyWRQV  LVWR p R[LJrQLR
FDUERQLODVKLGUR[LODVpWHUHV QLWURJrQLR DPLQDVHDPLGDV HKDORJrQLRV IO~RU
HFORUR 6mRLQFOXtGDVQDVIRUoDVGRWLSRiFLGREDVHRXIRUoDVGH/HZLV

$V OLJDo}HV SULPiULDV H VHFXQGiULDV VmR FDUDFWHUL]DGDV SHODV GLVWkQFLDV


LQWHUDW{PLFDV RX VHMD D GLVWkQFLD yWLPD HQWUH RV iWRPRV VHP TXH KDMD UHSXOVmR
HQWUH HOHV $ 7DEHOD  H[HPSOLILFD RV WLSRV GH LQWHUDo}HVOLJDo}HV DVVRFLDGRV jV
GLVWkQFLDVLQWHUDW{PLFDVHHQHUJLDGHGLVVRFLDomR

&DUDFWHUL]DomRGH3ROtPHURV 
2FDVRPDLVVLPSOHVpDTXHOHRQGHDVVROXo}HVH[LEHPVRPHQWHLQWHUDo}HVGR
WLSRYDQGHU:DDOV6HRVOtTXLGRVVmRDSRODUHVRXVHMDRPRPHQWRGLSRODUp]HUR
VyH[LVWHPIRUoDVGHGLVSHUVmRHQWUHHOHV8VXDOPHQWHHVWHVOtTXLGRVVHPLVWXUDP
EHP HP XPD ODUJD IDL[D GH WHPSHUDWXUD 3RU H[HPSOR SROLKLGURFDUERQHWRV
DPRUIRVDSRODUHV SROLLVREXWLOHQRSROLLVRSUHQRHSROLEXWDGLHQR VHGLVVROYHPEHP
HPKLGURFDUERQHWRVGHEDL[RSHVRPROHFXODU7DLVSROtPHURVQmRVHGLVVROYHPHP
OtTXLGRV SRODUHV FRPR DFHWRQD H HVSHFLDOPHQWH HP OtTXLGRV FDSD]HV GH IRUPDU
OLJDo}HV KLGURJrQLR 3RU RXWUR ODGR SROtPHURV TXH FRQWrP JUXSRV SRODUHV
SROLDFULORQLWULOD QmRVHGLVVROYHPHPVROYHQWHVDSRODUHV
7DEHOD'LVWkQFLDLQWHUDW{PLFDHHQHUJLDGHGLVVRFLDomRHPIXQomRGRWLSRGHOLJDomRHQWUHPROpFXODV

'LVWkQFLD (QHUJLDGHGLVVRFLDomR
7LSRVGHOLJDomR
LQWHUDW{PLFD c  .FDOPRO 
&RYDOHQWH  
/LJDomRL{QLFD  
/LJDomRKLGURJrQLR  
,QWHUDomRGLSRODU  
YDQGHU:DDOV  

2.5.2 Peso molecular dos polmeros


$FDSDFLGDGHGHXPSROtPHURHPVHGLVVROYHUVHPSUHGHFUHVFHFRPRDXPHQWRGR
VHX SHVR PROHFXODU HP TXDOTXHU VpULH KRPyORJD 0HPEURV GH EDL[R SHVR
PROHFXODU GH XPD VpULH SRGHP VH GLVVROYHU LQILQLWDPHQWH HP XP GHWHUPLQDGR
VROYHQWH HQTXDQWR TXH DTXHOHV GH DOWR SHVR PROHFXODU SRGHP DSHQDV VRIUHU
LQFKDPHQWR,VWRpGHYLGRjJUDQGHHQHUJLDGHLQWHUDomRFULDGDDRORQJRGDFDGHLD
SROLPpULFDHjPDLRUGLILFXOGDGHGHPRELOLGDGHGDVXQLGDGHVGHFDGHLDVFRQHFWDGDV
SRU OLJDo}HV FRYDOHQWHV (VWD GLIHUHQoD GH VROXELOLGDGH HP IXQomR GR SHVR
PROHFXODUWHPJUDQGHXWLOLGDGHQRIUDFLRQDPHQWRGHSROtPHURV

2.5.3 Flexibilidade das cadeias polimricas


2 PHFDQLVPR GH GLVVROXomR GH XP SROtPHUR FRQVLVWH QD VHSDUDomR GDV FDGHLDV
HQWUH VL H GH VXD GLIXVmR GHQWUR GR VROYHQWH $PERV RV SURFHVVRV GHSHQGHP GD
IOH[LELOLGDGHGDVFDGHLDV6HDVFDGHLDVVmRIOH[tYHLVHODVSRGHPVHPRYHUDWUDYpV
GH VXFHVVLYRV GHVORFDPHQWRV GH JUXSRV GH XQLGDGHV RX VHJPHQWRV 1HVWH FDVR D
HQHUJLDQHFHVViULDSDUDDVHSDUDomRpPHQRUHpVXSHUDGDSHODHQHUJLDOLEHUDGDQD
LQWHUDomR SROtPHURVROYHQWH 3RU HVWD UD]mR SROtPHURV IOH[tYHLV TXH VmR DSRODUHV
VmRXVXDOPHQWHPLVFtYHLVHPOtTXLGRVDSRODUHV
&DGHLDV UtJLGDV PRYHPVH SRU LQWHLUR H VXD VHSDUDomR UHTXHU XPD HQHUJLD
PDLRU$WHPSHUDWXUDVXVXDLVDHQHUJLDGHLQWHUDomRGRVVHJPHQWRVGDVFDGHLDVGR

 ,QWURGXomRDR&RPSRUWDPHQWRGH6ROXo}HVGH3ROtPHURV
SROtPHUR FRP R VROYHQWH QHP VHPSUH p JUDQGH R VXILFLHQWH SDUD VHSDUiODV
FRPSOHWDPHQWH 3ROtPHURV OLQHDUHV DPRUIRV FXMD ULJLGH] p GHYLGD j SUHVHQoD GH
JUXSRV SRODUHV LQFKDP EHP HP OtTXLGRV DOWDPHQWH SRODUHV SRUpP QmR VH
GLVVROYHP D WHPSHUDWXUDV XVXDLV 3DUD GLVVROYHU SROtPHURV PXLWR UtJLGRV p
QHFHVViULRTXHKDMDXPDIRUWHLQWHUDomRHQWUHRSROtPHURHRVROYHQWH3ROLDPLGDV
Q\ORQ SRUH[HPSORVyVHGLVVROYHPEHPHPiFLGRIyUPLFRGHYLGRjIRUPDomRGH
OLJDo}HVKLGURJrQLRHQWUHRSROtPHURHRVROYHQWH

2.5.4 Empacotamento das macromolculas


8PD YH] TXH D HQHUJLD GH LQWHUDomR GHSHQGH GD GLVWkQFLD LQWHUPROHFXODU
SROtPHURVFXMDVFDGHLDVDSUHVHQWDPPHOKRUHPSDFRWDPHQWRVmRPHQRVVRO~YHLV$
EDL[DVROXELOLGDGHGRSROLHWLOHQRLOXVWUDHVWHFDVR

2.5.5 Heterogeneidade relativa composio qumica do polmero


$FRPSRVLomRTXtPLFDGHPXLWRVSROtPHURVGLIHUHGHSHQGHQGRGDVXDFRQGLomRGH
SUHSDUDomR 3RU H[HPSOR DPRVWUDV GLIHUHQWHV GH DFHWDWR GH FHOXORVH SRGHP WHU
GLIHUHQWHVJUDXVGHDFHWLODomR$PRVWUDVGHSROL iOFRROYLQtOLFR SRGHPDSUHVHQWDU
GLIHUHQWHV JUDXV GH VDSRQLILFDomR HWF (VWHV SROtPHURV SRVVXHP GLIHUHQWHV
VROXELOLGDGHV GHYLGR j SUHVHQoD GH GLIHUHQWHV JUXSRV IXQFLRQDLV 3RU H[HPSOR
DFHWDWR GH FHOXORVH FRQWHQGR  GH JUXSRV DFHWLOD p PLVFtYHO HP DFHWRQD
HQTXDQWRTXHRWULDFHWDWRGHFHOXORVHpPLVFtYHOHPiFLGRDFpWLFRHiFLGRIyUPLFR
PDVVRPHQWHSDUFLDOPHQWHVRO~YHOHPDFHWRQD

2.5.6 Estrutura cristalina de polmeros


3DUDTXHXPSROtPHURFULVWDOLQRVHGLVVROYDpQHFHVViULRGHVWUXLUDUHGHFULVWDOLQD
HLVWRUHTXHUHQHUJLD(QWmRjWHPSHUDWXUDDPELHQWHSROtPHURVFULVWDOLQRVVmRHP
JHUDO LQVRO~YHLV PHVPR HP OtTXLGRV GH SRODULGDGH VHPHOKDQWHV 3RU H[HPSOR D
& R SROLHWLOHQR LQFKD OLPLWDGDPHQWH HP QKH[DQR 2 SROLHVWLUHQR LVRWiWLFR
FULVWDOLQR QmR VH GLVVROYH j WHPSHUDWXUD DPELHQWH HP VROYHQWHV XVXDLV SDUD R
SROLHVWLUHQR DWiWLFR 2 SROL WHWUDIOXRURHWLOHQR  p LQVRO~YHO HP WRGRV RV VROYHQWHV
FRQKHFLGRVHPWRGDVDVWHPSHUDWXUDV

2.5.7 Reticulao qumica


0HVPRXPQ~PHURSHTXHQRGHOLJDo}HVFUX]DGDVHQWUHDVFDGHLDVpVXILFLHQWHSDUD
LPSHGLUDVHSDUDomRGHVWDVHVXDSDVVDJHPSDUDDVROXomR3DUDID]HUXPSROtPHUR
LQVRO~YHOpQHFHVViULRFULDUDSHQDVXPDOLJDomRHQWUHGXDVFDGHLDV
6H D TXDQWLGDGH GH UHWLFXODomR HP XP SROtPHUR p UHODWLYDPHQWH EDL[D DV
PROpFXODVGHEDL[RSHVRPROHFXODU VROYHQWH SRGHPSHQHWUDUQDIDVHGHSROtPHUR
'HVWD IRUPD XP SROtPHUR UHWLFXODGR SRGH VRIUHU LQFKDPHQWR OLPLWDGR

&DUDFWHUL]DomRGH3ROtPHURV 
$XPHQWDQGR D GHQVLGDGH GH UHWLFXODomR D FDSDFLGDGH GH DEVRUomR GH OtTXLGR GH
EDL[R SHVR PROHFXODU GLPLQXL 4XDQGR RV VHJPHQWRV TXH IRUPDP R UHWtFXOR VmR
PXLWRSHTXHQRVRSROtPHURSHUGHFRPSOHWDPHQWHDFDSDFLGDGHGHLQFKDU

2.5.8 Temperatura
(VWH IDWRU p PXLWR LPSRUWDQWH QD GHILQLomR GRV SDUkPHWURV TXH GHILQHP D
VROXELOLGDGH GH XP SROtPHUR TXH SRGH PHOKRUDU RX SLRUDU FRP D YDULDomR GD
WHPSHUDWXUD2VVLVWHPDVSROtPHURVROYHQWHJHUDOPHQWHDSUHVHQWDPGLDJUDPDVGH
IDVH FDUDFWHUtVWLFRV FRP WHPSHUDWXUDV FUtWLFDV ([HPSORV VmR VLVWHPDV SROtPHUR
VROYHQWH TXH DSUHVHQWDP WHPSHUDWXUD FRQVROXWD VXSHULRU 8&67  RX WHPSHUDWXUD
FRPVROXWDLQIHULRU /&67 $)LJXUDLOXVWUDHVWHVGRLVFDVRV&RPRH[HPSORVGH
8&67SRGHVHFLWDUDFHWDWRGHFHOXORVHWHWUDFORURHWDQRSROLHVWLUHQRFLFORKH[DQRH
SROLLVREXWLOHQREHQ]HQRHQWUHRXWURV(VVHVVLVWHPDVFRPRDTXHFLPHQWRIRUPDP
VROXo}HVKRPRJrQHDV )LJXUDD 
+i FDVRV HP TXH R DTXHFLPHQWR SURGX] VHSDUDomR GH IDVH 2 SROtPHUR VDL GH
VROXomR (VWHV VLVWHPDV DSUHVHQWDP FRPSRUWDPHQWR GR WLSR /&67 )LJXUD E 
6LVWHPDVTXHSRVVXHPLQWHUDo}HVIRUWHVGRWLSROLJDomRKLGURJrQLRHQWUHSROtPHUR
VROYHQWHFRVWXPDPDSUHVHQWDUHVWHFRPSRUWDPHQWRWHPSHUDWXUDPDLVEDL[DD
IRUWH LQWHUDomR SROtPHURVROYHQWH SHUPLWH XPD ERD PLVFLELOLGDGH HQWUH HOHV
4XDQGRDTXHFLGRDVLQWHUDo}HVGRWLSROLJDomRKLGURJrQLRVmRURPSLGDVGHYLGRj
PRELOLGDGHWpUPLFD,VWRUHVXOWDHPVHSDUDomRGHIDVH

)LJXUD(IHLWRGDWHPSHUDWXUDQRFRPSRUWDPHQWRGHVROXo}HVSROLPpULFDVHPIXQomRGDFRPSRVLomR

 ,QWURGXomRDR&RPSRUWDPHQWRGH6ROXo}HVGH3ROtPHURV
2.6 Parmetro de solubilidade
$ SRODULGDGH GH XPD VXEVWkQFLD p XVXDOPHQWH FDUDFWHUL]DGD SHOR YDORU GD
FRQVWDQWH GH PRPHQWR GLSRODU TXH WRGDYLD QmR p XPD PHGLGD HIHWLYD GD
SRODULGDGH 3RU H[HPSOR WRGRV RV iOFRRLVDOLIiWLFRV RX WRGDV DV FHWRQDV SRVVXHP
SUDWLFDPHQWHRPHVPRPRPHQWRGLSRODUHWHPDomRGLIHUHQWHFRPRVROYHQWHFRP
UHVSHLWR D RXWURV OtTXLGRV RX SROtPHURV H TXH GHSHQGHP GR FRPSULPHQWR GR
UDGLFDO DOTXLOD 3DUD XP PHVPR YDORU GH PRPHQWR GLSRODU TXDQWR PDLRU IRU R
UDGLFDODOTXLODPHOKRULUiGLVVROYHURXLQFKDUXPSROtPHURDSRODU
&RPRPHGLGDGDLQWHUDomRLQWHUPROHFXODUXVDVHIUHTHQWHPHQWHRSDUkPHWURGH
VROXELOLGDGH GH +LOGHEUDQG  TXH p UHODFLRQDGR FRP D GHQVLGDGH GH HQHUJLD
R R
FRHVLYD &('  GH XP OtTXLGR SHOD UHODomR VLPSOHV    (L  9L  RQGH (L  p D
HQHUJLDGHYDSRUL]DomRGROtTXLGRH9LVHXYROXPHPRODU
o
(Ei /Vi) densidade de energia coesiva (2.18)

o
(Ei / Vi) parmetro de solubilidade (2.19)

2 SDUkPHWUR GH VROXELOLGDGH SRGH VHU UHODFLRQDGR DR + DWUDYpV GD VHJXLQWH
UHODomR
2
H = V1V2(1 - 2)  (2.20)

RQGH 9 H 9 VmR UHVSHFWLYDPHQWH DV IUDo}HV HP YROXPH GR VROYHQWH H GR
SROtPHUR H  VmRUHVSHFWLYDPHQWHRVSDUkPHWURVGHVROXELOLGDGHGRVROYHQWH
HGRSROtPHUR
$7DEHODIRUQHFHYDORUHVGHSDUDDOJXQVOtTXLGRVXVDGRVFRPRVROYHQWHVH
SDUD DOJXQV SROtPHURV %DL[RV YDORUHV GH  VmR FDUDFWHUtVWLFRV GH VXEVWkQFLDV
DSRODUHV HQTXDQWR TXH DOWRV YDORUHV LQGLFDP VXEVWkQFLDV FRP JUDQGH PRPHQWR
GLSRODU RX FDSD]HV GH IRUPDU OLJDo}HV KLGURJrQLR (P SULPHLUD DSUR[LPDomR R
PHOKRU VROYHQWH SDUD XP SROtPHUR p DTXHOH FXMD &(' VHMD VLPLODU jTXHOD GR
SROtPHUR

&DUDFWHUL]DomRGH3ROtPHURV 
7DEHOD3DUkPHWURGHVROXELOLGDGHGHDOJXQVSROtPHURVHVROYHQWHV

6ROYHQWH  FDOFP  3ROtPHUR  FDOFP 


Q+H[DQR  %RUUDFKDGHVLOLFRQH 
7HWUDFORUHWRGHFDUERQR  3ROLLVREXWLOHQR 
$FHWDWRGHHWLOD  3ROLHWLOHQR 
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&ORURIyUPLR  3ROLHVWLUHQR 
7HWUDKLGURIXUDQR  3ROL PHWDFULODWRGH 
PHWLOD 
$FHWRQD  3ROL FORUHWRGHYLQLOD  
0HWDQRO  3ROL WHUHIWDODWRGH 
HWLOHQR 

7HRULFDPHQWHTXDQWRPHQRUIRUDGLIHUHQoD PDLRUVHUiDVROXELOL]DomR
GRSROtPHURQHVWHVROYHQWH,VWRQHPVHPSUHpYHUGDGH
$ GHQVLGDGH GH HQHUJLD FRHVLYD p XPD FDUDFWHUtVWLFD LQWHJUDO GD LQWHUDomR
LQWHUPROHFXODU HQTXDQWR TXH D DomR GR VROYHQWH RX PLVFLELOLGDGH GHSHQGH GD
SUHVHQoD GH JUXSRV IXQFLRQDLV HVSHFtILFRV RX VHMD GH LQWHUDo}HV HVSHFtILFDV TXH
LQFOXHP OLJDomR KLGURJrQLR RX OLJDo}HV GRDGRUDFHSWRU H TXH FDXVDP D IRUPDomR
GHFRPSOH[RVVROYDWDGRV
'RLVJUXSRVIXQFLRQDLVSDUWLFLSDPQDIRUPDomRGHOLJDomRKLGURJrQLRXPGHOHV
p GRDGRU JUXSR iFLGR  H RXWUR p DFHSWRU GH SUyWRQV JUXSR EiVLFR  $ VHJXLU p
DSUHVHQWDGDDFODVVLILFDomRDFHLWDGHDFRUGRFRPRWLSRGHOLJDomRKLGURJrQLR

*UXSRGRDGRUGH *UXSRDFHSWRUGH
&ODVVHGHFRPSRVWR
SUyWRQ SUyWRQ
$ 6LP 1mR
% 1mR 6LP
$% 6LP 6LP
1 1mR 1mR

$ FODVVH $ FRQVLVWH GH FRPSRVWRV TXH FRQWpP VRPHQWH GRDGRUHV GH SUyWRQV
FRPRFRPSRVWRVKDORJHQDGRVFXMRQ~PHURGHKDORJrQHRVpVXILFLHQWHSDUDDWLYDU
R KLGURJrQLR &+&O &+%U &+&O HWF  2 39& H R SROLFORURSUHQR SHUWHQFHP D
HVWDFODVVH
$ FODVVH % FRQVLVWH GH FRPSRVWRV TXH FRQWHP VRPHQWH DFHSWRUHV GH SUyWRQV
FHWRQDV DOGHtGRV pWHUHV pVWHUHV DPLQDV WHUFLiULDV ROHILQDV EHQ]HQR H RXWURV

 ,QWURGXomRDR&RPSRUWDPHQWRGH6ROXo}HVGH3ROtPHURV
FRPSRVWRVDURPiWLFRVDFHSWRUHVGHSUyWRQVVmRiWRPRVGRWLSR21H)2SROL WH
WUDIOXRURHWLOHQR RSROL DFHWDWRGHYLQLOD HRVSROLDFULODWRVSHUWHQFHPDHVWDFODVVH
$FODVVH$%FRQVLVWHGHFRPSRVWRVTXHFRQWHPJUXSRVDFHSWRUHVHGRDGRUHVGH
SUyWRQV FRPR iOFRRLV iFLGRV DPLGDV R[LPDV DPLQDV SULPiULDV H VHFXQGiULDV H
iJXD'HQWUHRVSROtPHURVGHVWDFDPVHRSROL iOFRROYLQtOLFR RSROL iFLGRDFUtOLFR 
RSROL iFLGRPHWDFUtOLFR HDVSROLDPLGDV
$ FODVVH 1 FRQVLVWH GH FRPSRVWRVTXH QmR SRVVXHP TXDOTXHU JUXSR FDSD] GH
IRUPDUOLJDomRKLGURJrQLRFRPRKLGURFDUERQHWRVVDWXUDGRV
&RPSRVWRVGDFODVVH1PLVWXUDPVHEHPFRPFRPSRVWRVGDPHVPDFODVVH3DUD
WDLVVXEVWkQFLDVRWLSRSULQFLSDOGHLQWHUDomRpGLVSHUVmR
$VPROpFXODVGDFODVVH$H%QmRIRUPDPOLJDo}HVKLGURJrQLRFRPVHPHOKDQWHV
SRUpP IRUPDP SRQWHV XPDV FRP DV RXWUDV 3ROtPHURV TXH Vy SRVVXHP JUXSRV
DFHSWRUHVRXGRDGRUHVHPJHUDOQmRVHDVVRFLDPSRUOLJDo}HVKLGURJrQLRSRUpP
SRGHPIRUPDUSRQWHVFRPOtTXLGRVGDFODVVH$%RX$%
3ROtPHURV FRQWHQGR DPERV RV WLSRV GH JUXSRV VmR FDSD]HV GH VH GLVVROYHUHP
OtTXLGRVGRWLSR$%RX$%HDGLVVROXomRYDLGHSHQGHUGDFRUUHODomRGHIRUoDVGDV
OLJDo}HV KLGURJrQLR HQWUH SROtPHURSROtPHUR SROtPHURVROYHQWH H VROYHQWH
VROYHQWH 3RU H[HPSOR R SROL iOFRRO YLQtOLFR  SHUWHQFH j FODVVH $% H p FDSD] GH
LQWHUDJLU FRP iJXD RX iOFRRLV GH SHVR PROHFXODU EDL[R PDV D FDSDFLGDGH GH VH
GLVVROYHUGHSHQGHGDWHPSHUDWXUD
$OpPGLVVRRFDUiWHUGRDGRUDFHSWRU FRRUGHQDomR pPXLWRLPSRUWDQWHQDGLV
VROXomR GH SROtPHURV H XP FHUWR WLSR GH OLJDomR p IRUPDGD VH XP FRPSRQHQWH p
FDSD]GHGRDUXPSDUGHHOpWURQVHQTXDQWRTXHRXWURSRVVXLRUELWDOYD]LRFDSD]
GH DFHLWiOR $ FDSDFLGDGH GH XP VROYHQWH HP GRDU XP SDU GH HOpWURQV p FDUDF
WHUL]DGDSHORQ~PHURGRDGRUGHWHUPLQDGRDSDUWLUGHFHUWRVDFHSWRUHVSDGU}HV1D
7DEHODREVHUYDVHRQ~PHURGRDGRUGHYiULRVVROYHQWHVFRPUHODomRDR6E&O
&RQVLGHUDQGR RV GDGRV GD 7DEHOD  SRGHVH GL]HU TXH XP GHWHUPLQDGR
SROtPHURQmRQHFHVVDULDPHQWHLUiGLVVROYHUVHHPXPVROYHQWHFRPSDUkPHWURGH
VROXELOLGDGHVHPHOKDQWH2SDUkPHWURGHVROXELOLGDGHpXPDFDUDFWHUtVWLFDLQWHJUDO
GDVLQWHUDo}HVLQWHUPROHFXODUHVHQTXDQWRTXHDDomRGRVROYHQWHGHSHQGHGDSUp
VHQoD GH LQWHUDo}HV HVSHFtILFDV (QWUHWDQWR RV YDORUHVGH  SRGHP VHU XWLOL]DGRV
SDUD SUHYHU D LQVROXELOLGDGH GH SROtPHURV HP VROYHQWHV FRP YDORUHV GH  EHP
GLIHUHQWHV

&DUDFWHUL]DomRGH3ROtPHURV 
7DEHOD1~PHURGRDGRUGHYiULRVVROYHQWHVFRPUHODomRDR6E&O

1~PHUR 3DUkPHWURGHVROXELOLGDGH
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6ROYHQWH GRDGRU 
GLHOpWULFD
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1LWUREHQ]HQR   
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JXD   
7HWUDKLGURIXUDQR   
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6XOIy[LGRGH
  
GLPHWLOD

2.7 Dimenses no-perturbadas de macromolculas


$V GLPHQV}HV GH XPD PDFURPROpFXOD HP VROXomR QmR SRGHP VHU GHILQLGDV GH
IRUPDDEVROXWDSRUTXHDIRUPDGRQRYHORPROHFXODUDOWHUDVHHPIXQomRGRWHPSR
HGDVLQWHUDo}HVHQWUHSROtPHURHVROYHQWH2WDPDQKRPROHFXODUYDULDGHPROpFXOD
SDUD PROpFXOD PHVPR FRP HVWUXWXUDV H SHVRV PROHFXODUHV LGrQWLFRV 3RUWDQWR
SRGHVHUGHILQLGRVRPHQWHHPWHUPRVGHSURSULHGDGHVPpGLDV
8PD PDFURPROpFXOD HP VROXomR DVVXPH XPD IRUPD HQRYHODGD $V GLPHQV}HV
GHVWH QRYHOR GHSHQGHUmR VXEVWDQFLDOPHQWH GDV LQWHUDo}HV HQWUH SROtPHUR H
VROYHQWH4XDQGRH[LVWHXPDERDLQWHUDomRHQWUHSROtPHURHVROYHQWHDVPROpFXODV
GHVROYHQWHSHQHWUDPIDFLOPHQWHQRQRYHORSROLPpULFRH[SDQGLQGRR&RPLVWRR
WDPDQKRPROHFXODUpEHPPDLRUGRTXHVHULDVHRQRYHORHVWLYHVVHHQFROKLGR3RU
RXWUR ODGRVHDVLQWHUDo}HVHQWUHDVPROpFXODVGRVROYHQWHHDVGRSROtPHURQmR
IRUHP PXLWR HILFLHQWHV R QRYHOR SROLPpULFR WHQGH D ILFDU PHQRU SRUTXH D
WHQGrQFLDGDVPROpFXODVGRVROYHQWHHPSHQHWUDUQRQRYHORpPHQRU
2WDPDQKRTXHXPDPDFURPROpFXODDVVXPHHPVROXomRGLOXtGDpGHQRPLQDGR
YROXPHKLGURGLQkPLFR
2V SULQFLSDLV SDUkPHWURV TXH GHILQHP R WDPDQKR PROHFXODU GH XPD
PDFURPROpFXODOLQHDUHPVROXomRVmR
(r 2 ) 
( )
SGLVWkQFLDH[WUHPRDH[WUHPRTXDGUiWLFDPpGLD
2
SUDLRGHJLUDomRTXDGUiWLFRPpGLR s 

$ )LJXUD  PRVWUD XPD UHSUHVHQWDomR GH XP QRYHOR PROHFXODU VLPSOHV SDUD
XPD PDFURPROpFXOD OLQHDU 2 FHQWUR GH JUDYLGDGH GD PDFURPROpFXOD HVWi
ORFDOL]DGRQRSRQWR22UDLRGHJLUDomR6FRUUHVSRQGHjGLVWkQFLDHQWUHRFHQWUR
GHJUDYLGDGH2HDVXSHUItFLHGDHVIHUDTXHFRQWpPRQRYHOR2WHUPRUpGHILQLGR

 ,QWURGXomRDR&RPSRUWDPHQWRGH6ROXo}HVGH3ROtPHURV
FRPR D GLVWkQFLD HQWUH DV H[WUHPLGDGHV GD FDGHLD 2 SDUkPHWUR U Vy SRGH VHU
XWLOL]DGR SDUD PDFURPROpFXODV OLQHDUHV 0DFURPROpFXODV UDPLILFDGDV DSUHVHQWDP
YiULDV H[WUHPLGDGHV GH FDGHLD H SRUWDQWR R VHX WDPDQKR PROHFXODU Vy SRGH VHU
GHILQLGRSHORUDLRGHJLUDomR

)LJXUD5HSUHVHQWDomRHVTXHPiWLFDGHXPQRYHORPDFURPROHFXODU

$ GLVWkQFLD H[WUHPRDH[WUHPR TXDGUiWLFD PpGLD HQWUH DV H[WUHPLGDGHV GD


FDGHLDGHXPDPDFURPROpFXODOLQHDU (r 2 ) pGDGDSHODIyUPXOD

r 2 = ro2 2 (2.21)

( )
RQGH U pDGLVWkQFLDH[WUHPRDH[WUHPRTXDGUiWLFDPpGLDHQWUHDVH[WUHPLGDGHV
GDFDGHLDPHGLGRHPFRQGLo}HVQmRSHUWXUEDGDVHpRFRHILFLHQWHGHH[SDQVmR




&DUDFWHUL]DomRGH3ROtPHURV 
( )
2UDLRGHJLUDomRTXDGUiWLFRPpGLR s 2 pGDGRSHODHTXDomR

s 2 = so2 2 (2.22)

RQGH so2  p R UDLR GH JLUDomR TXDGUiWLFR PpGLR PHGLGR HP FRQGLo}HV QmR
SHUWXUEDGDVHpRFRHILFLHQWHGHH[SDQVmR
3DUDSROtPHURVOLQHDUHVDVHJXLQWHUHODomRHQWUHUHVSRGHVHUXWLOL]DGD

r 2 = 6s2 (2.23)

'LPHQV}HV SHUWXUEDGDV VmR DV GLPHQV}HV GD FDGHLD HP XP GHWHUPLQDGR
VROYHQWHRQGHRFRUUHPLQWHUDo}HVLQWHUPROHFXODUHVHQWUHRSROtPHURHRVROYHQWH
'LPHQV}HV QmRSHUWXUEDGDV VmR DTXHODV LQIOXHQFLDGDV VRPHQWH SHORV
FRPSULPHQWRV GH OLJDomR H kQJXORV GH OLJDomR GD PDFURPROpFXOD $V GLPHQV}HV
QmRSHUWXUEDGDV VmR DOFDQoDGDV TXDQGR DV LQWHUDo}HV SROtPHURSROtPHUR
SROtPHURVROYHQWH H VROYHQWHVROYHQWH VmR VHPHOKDQWHV RX VHMD QmR H[LVWH
LQWHUDomRSUHIHUHQFLDO(VWDFRQGLomRpGHILQLGDFRPRFRQGLomRWHWD  HGHSHQGH
GR SDU SROtPHURVROYHQWH H GD WHPSHUDWXUD 6ROXo}HV VRE FRQGLo}HV WHWD
DSUHVHQWDPFRPSRUWDPHQWRLGHDO
$V GLPHQV}HV GH XPD PDFURPROpFXOD VmR GHILQLGDV D SDUWLU GH GRLV WLSRV GH
LQWHUDomRGHVFULWRVDVHJXLU
D  ,QWHUDo}HVGHFXUWRDOFDQFHHVWDVLQWHUDo}HVLQIOXHQFLDPDURWDomRLQWHUQDGD
PDFURPROpFXOD GHYLGR D UHVWULo}HV GH kQJXORV GH OLJDomR H
HVWHUHRLPSHGLPHQWR $ PHGLGD GR HIHLWR GHVWDV LQWHUDo}HV GH FXUWR DOFDQFH p
GDGDSHODTXDQWLGDGH&\GHILQLGDFRPR

C = lim ro2
n
n l
i
i i (2.24)

RQGHQLpRQ~PHURGHLWLSRVGHOLJDomRGHFRPSULPHQWROL
E  ,QWHUDo}HV GH ORQJR DOFDQFH  VmR LQWHUDo}HV TXH GHSHQGHP GDV LQWHUDo}HV
SROtPHURVROYHQWHHVmRGHWHUPLQDGDVSHORFRHILFLHQWHGHH[SDQVmRHSHOR
SDUkPHWURGHYROXPHH[FOXtGR ] (VWHVSDUkPHWURVVmRFRUUHODFLRQDGRVDSDUWLU
GDVHJXLQWHHTXDomR

lim x
= c te
z (2.25)
x

 ,QWURGXomRDR&RPSRUWDPHQWRGH6ROXo}HVGH3ROtPHURV
RQGH [ p XPD FRQVWDQWH TXH LQGHSHQGH GH ] 9DORUHV GH [ HQWUH  H  IRUDP
SUHYLVWRVDSDUWLUGHGLIHUHQWHVWHRULDV
2 IDWRU GH H[SDQVmR  p GHILQLGR FRPR D UD]mR GDV GLPHQV}HV GDFDGHLDHP
XPGHWHUPLQDGRVROYHQWH GLPHQV}HVSHUWXUEDGDV HHPVROYHQWHWHWD GLPHQV}HV
QmRSHUWXUEDGDV DXPDWHPSHUDWXUDHVSHFtILFD

(r ) 2 1 2
(s ) 2 1 2

a = =
(r ) (s )
2 1 2 2 1 2
(2.26)
0 0

2IDWRUGHH[SDQVmRpWDPEpPIXQomRGRSRGHUGRVROYHQWH6HRSROtPHURHVWi
HP XP ERP VROYHQWH R IDWRU GH H[SDQVmR  p PDLRU GR TXH D XQLGDGH ,VWR
VLJQLILFD TXH DV GLPHQV}HV SHUWXUEDGDV UHDLV VmR PDLRUHV GR TXH DV GLPHQV}HV
QmRSHUWXUEDGDV
2 IDWRU GH H[SDQVmR DXPHQWD FRP R SHVR PROHFXODU ,VWR RFRUUH SRUTXH R
Q~PHUR GH LQWHUDo}HV QmR FRPSHQVDGDV HQWUH RV VHJPHQWRV GD FDGHLD DXPHQWD
FRPRQ~PHURGHVHJPHQWRVTXDQGRDWHPSHUDWXUDpPDLRUGRTXHDWHPSHUDWXUD
WHWD
&DGDPROpFXODHPXPDVROXomRPXLWRGLOXtGDHPXPERPVROYHQWHSRVVXLXPD
WHQGrQFLD D H[FOXLU WRGDV DV RXWUDV GR YROXPH TXH HOD RFXSD $ SDUWLU GHVWH
IHQ{PHQR p GHILQLGR R WHUPR YROXPH H[FOXtGR R TXDO p R UHVXOWDGR GD UHSXOVmR
HQWUHDVPROpFXODVGRSROtPHURGHYLGRDUHTXLVLWRVHVSDFLDLV
0DFURPROpFXODV UDPLILFDGDV SRVVXHP XPD GHQVLGDGH PpGLD GH VHJPHQWRV
PDLRU GR TXH PDFURPROpFXODV OLQHDUHV GH SHVRV PROHFXODUHV VHPHOKDQWHV H SRU
LVVRDVSULPHLUDVSRVVXHPXPQRYHORFRPYROXPHPHQRU
2 Q~PHUR GH SRQWRV GH UDPLILFDomR HP XPD PDFURPROpFXOD UDPLILFDGD J  p
GHWHUPLQDGR SHOD UD]mR HQWUH DV GLPHQV}HV GH FDGHLD GD PDFURPROpFXOD
UDPLILFDGD H GD PDFURPROpFXOD OLQHDU GH PHVPR SHVR PROHFXODU H HP VROYHQWH
WHWD

s o2B
g = 2 (2.27)
soL
$ GHWHUPLQDomR GH GLPHQV}HV QmRSHUWXUEDGDV SRGH VHU IHLWD D SDUWLU GH
WpFQLFDV FRPR YLVFRVLGDGH H HVSDOKDPHQWR GH OX] GH VROXo}HV GLOXtGDV GH
SROtPHURVDVTXDLVVHUmRGLVFXWLGDVHPFDStWXORVSRVWHULRUHV

&DUDFWHUL]DomRGH3ROtPHURV 
Bibliografia recomendada
$EXLQ(6/LVVL(**DUJDOOR/*H5DGLF')0DFURPROpFXODVHQ6ROXFLyQ
81(6&26DQWLDJR
%LOOPH\HU -U ) :   7H[WERRN RI 3RO\PHU 6FLHQFH D HG -RKQ :LOH\  6RQV
,QF1HZ<RUN
&DVWHOODQ*:3K\VLFDO&KHPLVWU\$GGLVRQ:HVOH\3XEOLVKLQJ&RPSDQ\,QF
/RQGRQ
&RZLH-0*3RO\PHUV&KHPLVWU\DQG3K\VLFVRI0RGHUQ0DWHULDOV%ODFNLH 
6RQ/WG*ODVJRZ
(OLDV +*  0DFURPROHFXOHV  6WUXFWXUH DQG 3URSHUWLHV 3OHQXP 3UHVV 1HZ
<RUN
0DQR ( % H 0HQGHV / &  ,QWURGXomR D 3ROtPHURV D HG (GLWRUD (GJDUG
%OXFKHU/WGD6mR3DXOR
0RRUH : - )tVLFR4XtPLFD 6mR 3DXOR $R /LYUR 7pFQLFR 6$  7UDGHP
SRUWXJXrV 
5DEHN - )  ([SHULPHQWDO 0HWKRGV LQ 3RO\PHU &KHPLVWU\ -RKQ :LOH\  6RQV
1HZ<RUN
9DQ.UHYHOHQ':H+RIW\]HU3-3URSHUWLHVRI3RO\PHUV(OVHYLHU3XEOLVKLQJ
&RPSDQ\$PVWHUGDP
9ROOPHUW%3RO\PHU&KHPLVWU\6SULQJHU9HUODJ%HUOLQ
7DJHU$3K\VLFDO&KHPLVWU\RI3RO\PHUV0,53XEOLVKHUV0RVFRZ


 ,QWURGXomRDR&RPSRUWDPHQWRGH6ROXo}HVGH3ROtPHURV
&DStWXOR

Definio de Peso
Molecular em Polmeros
$FDUDFWHUtVWLFDPDLVLPSRUWDQWHGRVSROtPHURVpRVHXWDPDQKRPROHFXODU2DOWR
SHVR PROHFXODU H D HVWUXWXUD TXtPLFD GRV PDWHULDLV SROLPpULFRV VmR RV SULQFLSDLV
UHVSRQViYHLVSHODVVXDVSURSULHGDGHVHFRQVHTHQWHPHQWHSHODVXDXWLOL]DomRHP
LQ~PHUDVDSOLFDo}HV
2SHVRPROHFXODUGHXPSROtPHURQmRSRGHVHUFDOFXODGRFRPRQRUPDOPHQWHp
IHLWR FRP FRPSRVWRV SXURV GH EDL[R SHVR PROHFXODU 3ROtPHURV QmR UHWLFXODGRV
HODVW{PHURV DQWHV RX DSyV D YXOFDQL]DomR H UHVLQDV  WHUPRUUtJLGDV FRQVLVWHP GH
XPDJUXSDPHQWRGHPROpFXODVGHYiULRVWDPDQKRVRXVHMDH[LEHPQRUPDOPHQWH
XPD GLVWULEXLomR GH SHVR PROHFXODU H VmR GHQRPLQDGRV SROLGLVSHUVRV (VWD
FDUDFWHUtVWLFD WHQGH D FRPSOLFDU D GHWHUPLQDomR GR SHVR PROHFXODU GH XP
SROtPHUR e QHFHVViULR SRUWDQWR HQFRQWUDU XP PHLR SDUD GHILQLU H GHWHUPLQDU R
VHXSHVRPROHFXODUHDVXDGLVWULEXLomRGHSHVRPROHFXODU(PSULPHLUROXJDUSHVR
PROHFXODU GH XP SROtPHUR GHWHUPLQDGR SRU TXDOTXHU XP GRV PpWRGRV GHVFULWRV
QRVSUy[LPRVFDStWXORVpQDYHUGDGHRSHVRPROHFXODUPpGLR2YDORUHQFRQWUDGR
VHUiIXQomRGRPpWRGRHVFROKLGRSDUDDVXDGHWHUPLQDomRFRPRYHUHPRVDGLDQWH
6HFRQVLGHUDUPRVXPDGLVWULEXLomRWtSLFDGHSHVRPROHFXODUWDOFRPRPRVWUDGD
QD)LJXUDpSRVVtYHOGHILQLUXPDVpULHGHYDORUHVGHSHVRPROHFXODU
8WLOL]DQGRVH PpWRGRV EDVHDGRV QR Q~PHUR GH PROpFXODV 1L  GD HVSpFLH L GH
SHVR PROHFXODU 0L REWpPVH YDORUHV GH SHVR PROHFXODU QXPpULFR PpGLR M Q H
TXHSRGHVHUGHILQLGRVHJXQGRD(TXDomR

N i Mi
Mn =
Ni (3.1)

&DUDFWHUL]DomRGH3ROtPHURV 
)LJXUD&XUYDWtSLFDGHGLVWULEXLomRGHSHVRPROHFXODUGHXPDDPRVWUDSROLPpULFD

(VWD GHILQLomR FRUUHVSRQGH DR FOiVVLFR FRQFHLWR GH SHVR PROHFXODU SDUD
PROpFXODVGHEDL[RSHVRPROHFXODUTXHSRVVXHPRPHVPRSHVRPROHFXODU2 M Q
SRGHUi VHU FDOFXODGR IDFLOPHQWH GHVGH TXH D PDVVD HP JUDPDV GD DPRVWUD
SROLPpULFD VHMD FRQKHFLGD H R Q~PHUR GH PROpFXODV GHVWH SROtPHUR SROLGLVSHUVR
SRVVD VHU GHWHUPLQDGR 0pWRGRV EDVHDGRV HP DQiOLVH GH JUXSR WHUPLQDO H HP
PHGLGDVGHSURSULHGDGHVFROLJDWLYDVIRUQHFHPRQ~PHURGHPROpFXODVSRUJUDPD
GR PDWHULDO H SRUWDQWR VmR XWLOL]DGRV SDUD D GHWHUPLQDomR GR SHVR PROHFXODU
QXPpULFRPpGLR
0pGLDVEDVHDGDVQDIUDomRHPSHVR ZL GDVPROpFXODVGHXPGHWHUPLQDGRSHVR
PROHFXODU 0L  FRQGX]HP j GHILQLomR GH SHVR PROHFXODU SRQGHUDO PpGLR M Z
GHVFULWDDVHJXLU

wi Mi N i Mi2
Mw = = (3.2)
wi N i Mi
9DORUHVGHSHVRPROHFXODUSRQGHUDOPpGLRVmRREWLGRVDWUDYpVGHPpWRGRVTXH
VmR PDLV VHQVtYHLV j SUHVHQoD GH PROpFXODV GH WDPDQKR PDLRU 2 PpWRGR PDLV
XVDGRSDUDWDOPHGLGDpDTXHOHEDVHDGRQRHVSDOKDPHQWRGHOX]
$OpP GRV SHVRV PROHFXODUHV PpGLRV GHVFULWRV DFLPD RXWUR SHVR PROHFXODU
PXLWR XVDGR SDUD GHVFUHYHU DV SURSULHGDGHV GH XP SROtPHUR p R SHVR PROHFXODU

 'HILQLomRGH3HVR0ROHFXODUHP3ROtPHURV
YLVFRVLPpWULFR PpGLR M Y FXMD GHILQLomR p GHVFULWD D VHJXLU 2V YDORUHV GH M Y
VmR REWLGRV D SDUWLU GH PHGLGDV GH YLVFRVLGDGH GH VROXo}HV SROLPpULFDV H HVWmR
PDLVSUy[LPRVGH M ZGRTXHGH M QSDUDXPSROtPHURSROLGLVSHUVR

[ ]
1
Ni Mi 1+

Mv =
Ni Mi (3.3)

0ROpFXODV GH EDL[R SHVR PROHFXODU DIHWDP PDLV RV YDORUHV GH M Q HQTXDQWR
TXH PROpFXODV GH SHVR PROHFXODU PDLV HOHYDGR LQIOXHQFLDP PDLV RV YDORUHV GH
M Z $ )LJXUD  LOXVWUD HVWH FRPSRUWDPHQWR $ SUHVHQoD GH XPD SHTXHQD
TXDQWLGDGH GH PROpFXODV GH DOWR SHVR PROHFXODU FXUYD %  UHVXOWD HP XP
DFUpVFLPR GH  QR YDORU GH M Z H GH DSHQDV  QR YDORU GH M Q 3RU RXWUR
ODGRFRPXPSHTXHQRDFUpVFLPRQRQ~PHURGHPROpFXODVGHEDL[RSHVRPROHFXODU
FXUYD& RYDORUGH M QGHFUHVFHHPFHUFDGHHQTXDQWRTXH M ZGHFUHVFH
DSHQDV
8PDYH]GHILQLGRVRVSHVRVPROHFXODUHVPpGLRVHFRQKHFLGRVRVPpWRGRVFDSD]HV
GHIRUQHFHURVYDORUHVFRUUHVSRQGHQWHVpQHFHVViULRHQWmRHVFROKHURPpWRGRDVHU
HPSUHJDGR QD FDUDFWHUL]DomR GH XPD DPRVWUD SROLPpULFD SDUWLFXODU 6H R HVWXGR
HQYROYHUSDUkPHWURVFLQpWLFRVGHSROLPHUL]DomRRSHVRPROHFXODUQXPpULFRPpGLR
pRPDLVLQGLFDGR M QpWDPEpPQHFHVViULRSDUDGHWHUPLQDUSRUH[HPSORRJUDX
GH IXQFLRQDOL]DomR HP SROtPHURV FRP JUXSRV IXQFLRQDLV HVSHFtILFRV (P iUHDV GD
FLrQFLD GH SROtPHURV PDLV DSOLFDGDV UHRORJLD SURSULHGDGHV PHFkQLFDV HWF  p
QHFHVViULR FRQKHFHU RV YDORUHV GH M Q M Z DOpP GD IRUPD H H[WHQVmR GD
GLVWULEXLomRGHSHVRPROHFXODU

&DUDFWHUL]DomRGH3ROtPHURV 
)LJXUD(IHLWRGDDGLomRGHSHTXHQDTXDQWLGDGHGHPDFURPROpFXODVGHEDL[R & RXDOWR % SHVR
PROHFXODUQRVYDORUHVGH M ZH M Q
$ GLVWULEXLomR GH SHVR PROHFXODU RX SROLGLVSHUVmR p GHWHUPLQDGD D SDUWLU GD
UD]mR 0  0 Q 3DUD DPRVWUDV PRQRGLVSHUVDV RV YDORUHV GH 0 Q H 0  VmR
Z Z

SUDWLFDPHQWHLGrQWLFRVHDSROLGLVSHUVmRpLJXDOjXQLGDGH
4XDQGR VH FRQVLGHUDP RV PpWRGRV LQVWUXPHQWDLV SDUD GHWHUPLQDomR GR SHVR
PROHFXODUpLPSRUWDQWHGLVWLQJXLUDTXHOHVTXHIRUQHFHPSHVRPROHFXODUDEVROXWR
GDTXHOHV PpWRGRV TXH QHFHVVLWDP FDOLEUDomR XWLOL]DQGRVH SDGU}HV GH SHVR
PROHFXODU FRQKHFLGR 0pWRGRV DEVROXWRV LQFOXHP PHGLGDV GH SURSULHGDGHV
FROLJDWLYDV SDUD GHWHUPLQDomR GH 0 Q H WpFQLFDV GH HVSDOKDPHQWR GH OX] SDUD
GHWHUPLQDomR GH 0  0pWRGRV TXH UHTXHUHP FDOLEUDomR LQFOXHP PHGLGDV GH
Z

YLVFRVLGDGH HP VROXomR H FURPDWRJUDILD GH H[FOXVmR SRU WDPDQKR (VWH ~OWLPR
IRUQHFHWDPEpPDGLVWULEXLomRGRSHVRPROHFXODU
$ PDLRULD GRV PpWRGRV GHVFULWRV D VHJXLU XWLOL]D SROtPHURV HP VROXomR
3ROtPHURVUHWLFXODGRVQmRVmRVRO~YHLVHPVROYHQWHDOJXPHRVHXSHVRPROHFXODU
QmRSRGHVHUGHWHUPLQDGR3RURXWURODGRDVVXPHVHTXHRSHVRPROHFXODUGHVWHV
SROtPHURV p LQILQLWR XPD YH] TXH WRGDV DV FDGHLDV SROLPpULFDV HVWDULDPOLJDGDV
HQWUHVLDWUDYpVGHOLJDo}HVFRYDOHQWHV
2V FDStWXORV D VHJXLU GHVFUHYHUmR DV GLYHUVDV WpFQLFDV SDUD GHWHUPLQDomR GH
SHVRPROHFXODUDSUHVHQWDGDVQD7DEHOD

 'HILQLomRGH3HVR0ROHFXODUHP3ROtPHURV

7DEHOD0pWRGRVXWLOL]DGRVSDUDGHWHUPLQDomRGRSHVRPROHFXODUGHSROtPHURV

$ $EVROXWR
0pWRGR 3HVRPROHFXODU
5 5HODWLYR
$QiOLVHGHJUXSRWHUPLQDO $ 0 Q
(EXOLRVFRSLDHFULRVFRSLD $ 0 Q
3UHVVmRRVPyWLFD $ 0 Q
2VPRPHWULDGHSUHVVmRGHYDSRU $  0 Q
(VSDOKDPHQWRGHOX] $ 0 Z
(VSDOKDPHQWRGHUDLRV;DEDL[R
$ 0 Z
kQJXOR
8OWUDFHQWULILJDomR $ 0 Z
9LVFRVLGDGH 5 0 Y
&URPDWRJUDILDGHH[FOXVmRSRU
5 0 QH 0 Z
WDPDQKR

$OJXQVDXWRUHVFRQVLGHUDPHVWHPpWRGRUHODWLYR

&DUDFWHUL]DomRGH3ROtPHURV 
Bibliografia recomendada
$EXLQ(6/LVVL(**DUJDOOR/*H5DGLF')0DFURPROpFXODVHQ6ROXFLyQ
81(6&26DQWLDJR
%LOOPH\HU-U):7H[WERRNRI3RO\PHU6FLHQFHDHG-RKQ:LOH\ 6RQV,QF
1HZ<RUN
&RZLH-0*3RO\PHUV&KHPLVWU\DQG3K\VLFVRI0RGHUQ0DWHULDOV%ODFNLH 
6RQ/WG*ODVJRZ
(OLDV +*  0DFURPROHFXOHV  6WUXFWXUH DQG 3URSHUWLHV 3OHQXP 3UHVV 1HZ
<RUN
5DEHN - )  ([SHULPHQWDO 0HWKRGV LQ 3RO\PHU &KHPLVWU\ -RKQ :LOH\  6RQV
1HZ<RUN
7DJHU$3K\VLFDO&KHPLVWU\RI3RO\PHUV0,53XEOLVKHUV0RVFRZ
9ROOPHUW%3RO\PHU&KHPLVWU\6SULQJHU9HUODJ%HUOLQ

 'HILQLomRGH3HVR0ROHFXODUHP3ROtPHURV
&DStWXOR

Tcnicas para
Determinao de Peso
Molecular Numrico Mdio

4.1 Anlise de grupo terminal


$DQiOLVHGHJUXSRVWHUPLQDLVHPXPDFDGHLDSROLPpULFDpRPpWRGRPDLVVLPSOHV
SDUD D GHWHUPLQDomR GH M n  (VWD p SDUWLFXODUPHQWH ~WLO SDUD SROtPHURV GH EDL[R
SHVRPROHFXODU  SRLVQHVWHFDVRDFRQFHQWUDomRGHJUXSRVWHUPLQDLVpDOWD
(VWDDQiOLVHSRGHVHUUHDOL]DGDSRUPpWRGRVTXtPLFRVHItVLFRV2VPpWRGRVTXtPLFRV
VmREDVHDGRVHPUHDo}HVTXtPLFDVFRPRVJUXSRVWHUPLQDLVWLWXODomRHWF0pWRGRV
ItVLFRVEDVHLDPVHSULQFLSDOPHQWHQDXWLOL]DomRGHHVSHFWURVFRSLDQRLQIUDYHUPHOKR
UHVVRQkQFLD PDJQpWLFD QXFOHDU HVSHFWURVFRSLD QR XOWUDYLROHWD HWF $SHQDV D
GHWHUPLQDomR GH SHVR PROHFXODU EDVHDGD QD DQiOLVH GH JUXSRV WHUPLQDLV SRU
WLWXODomRVHUiDERUGDGDQHVWHWySLFR
$ GHWHUPLQDomR GH M n  SRU WLWXODomR SRGH VHU XWLOL]DGD TXDQGR R SROtPHUR p
OLQHDU H SRVVXL JUXSRV IXQFLRQDLV WHUPLQDLV FDSD]HV GH VHUHP TXDQWLWDWLYDPHQWH
PHQVXUDGRV$OpPGLVWRpLPSRUWDQWHTXHQmRKDMDSHUGDGHVWHVJUXSRVSRUUHDo}HV
ODWHUDLV SRU H[HPSOR D FLFOL]DomR QR FDVR GH GHWHUPLQDGDV UHDo}HV GH
SROLFRQGHQVDomR RXDLQGDDIRUPDomRGHJUXSRVIXQFLRQDLVSRUUDPLILFDomR
(P SROtPHURV REWLGRV DWUDYpV GH WpFQLFDV GH SROLFRQGHQVDomR WDLV FRPR
SROLpVWHUHV H SROLDPLGDV D WLWXODomR GLUHWD p HIHWLYD QD GHWHUPLQDomR GH JUXSRV
WHUPLQDLV XPD YH] TXH HVWHV VmR UHDWLYRV 1HVWH WySLFR D GHWHUPLQDomR GH SHVR
PROHFXODUGHSROLpVWHUHVVHUiXWLOL]DGDFRPRH[HPSORHDSUHVHQWDGDDVHJXLU
1DUHDomRGHREWHQomRGHXPSROLpVWHUDSDUWLUGHXPDFRQGHQVDomRHPHWDSDV
GHXPGLiFLGRFRPXPGLiOFRROSUHVXPHVHTXHFDGDFDGHLDSROLPpULFDSRVVXDQD
PpGLD XP JUXSR FDUER[LOD &22+ H XP JUXSR KLGUR[LOD 2+ FRPR PRVWUD R
HVTXHPDDVHJXLU

&DUDFWHUL]DomRGH3ROtPHURV 
nHO-R-OH + nHOOC-R-COOH

HO-R-O-[OC-RCOO-R-O]n-1OC-R-COOH + (n-1)H2O
3DUDGHWHUPLQDURHTXLYDOHQWHJUDPDGHJUXSRV&22+H2+GHYHVHSURFHGHUD
XPDWLWXODomRGHVWHVJUXSRV
3ULPHLUDPHQWH SURFHGHVH XPD WLWXODomR GLUHWD GRV JUXSRV &22+ FRP VROXomR
SDGUmRGH.2+
-COOH + KOH -COOK + H2O
$ WLWXODomR GRV JUXSRV 2+ UHTXHU XPD SUpYLD DFHWLODomR GHVWHV FRP DQLGULGR
DFpWLFRVHJXLGDGHGRVDJHPGRiFLGRDFpWLFRDSyVKLGUyOLVHGRH[FHVVRGRUHDJHQWH
-OH + (CH3CO)2O -OOCCH3 + CH3COOH

CH3COOH + KOH CH3COOK + H2O


3DUD D GRVDJHP GRV JUXSRV WHUPLQDLV D VHJXLQWH PHWRGRORJLD SRGHUi VHU
DGRWDGD
S3HVDU FHUFD GH J GR SROLpVWHU D VHU DQDOLVDGR H GLVVROYrOR HP PO GH XPD
VROXomRGHDQLGULGRDFpWLFRHPSLULGLQD HPYROXPH 
S$TXHFHUDVROXomRSRUFHUFDGHXPDKRUDVREUHIOX[R
S$GLFLRQDUFHUFDGHP/GHiJXDSDUDKLGUROLVDURDQLGULGRDFpWLFRQmRUHDJLGR
S5HPRYHURFDORUDSyVFLQFRPLQXWRVGHUHDomRHDGLFLRQDUP/GHPHWDQRO
S7LWXODU R iFLGR DFpWLFR IRUPDGR FRP VROXomR SDGUmR GH .2+ XWLOL]DQGR
IHQROIWDOHLQDFRPRLQGLFDGRU

2YROXPHGDVROXomRGH.2+FRQVXPLGRpFKDPDGRYDORU$FDOFXODGRHPPJGH
.2+SRUJUDPDGHSROtPHUR
)D]VH HQWmR XPD WLWXODomR GH UHIHUrQFLD EUDQFR  RQGH WRGRV RV UHDJHQWHV
PHQRVRSROtPHURVmRDGLFLRQDGRVQRIUDVFRHRiFLGRDFpWLFRIRUPDGRpWLWXODGR2
YROXPHGDVROXomRGH.2+FRQVXPLGRQHVWDWLWXODomRHPEUDQFRpFKDPDGRGHYDORU
% PJ.2+JGHSROtPHUR 
2XWUD DPRVWUD GR PHVPR SROtPHUR p HQWmR WLWXODGD 'HVWD YH] p XWLOL]DGD D
WLWXODomRGLUHWDGRVJUXSRV&22+GLVVROYHQGRVHDDPRVWUDHPSLULGLQDHWLWXODQGR
VHFRPDPHVPDVROXomRSDGUmRGH.2+2YROXPHGDVROXomRGH.2+FRQVXPLGRQD
WLWXODomRGLUHWDpFKDPDGRYDORU& PJ.2+JGHSROtPHUR 
2 Q~PHUR GH HTXLYDOHQWHV GH JUXSR &22+ p R YDORU & HP PJ .2+J GR
SROtPHUR

 7pFQLFDVSDUD'HWHUPLQDomRGH3HVR0ROHFXODU1XPpULFR0pGLR
2Q~PHURGHHTXLYDOHQWHVGHJUXSR2+pLJXDOD>YDORU&YDORU%YDORU$@HP
PJ.2+JGHSROtPHUR
2SHVRPROHFXODUQXPpULFRPpGLRpGHWHUPLQDGRGDVHJXLQWHIRUPD
[No de COOH + No de OH]/ [2 x 56,1 x 1000] = moles de polmero por grama
M n  PROHVGHSROtPHURSRUJUDPD

2 PpWRGR p UHVWULWR D SROtPHURV GH EDL[R SHVR PROHFXODU $ VHQVLELOLGDGH GR


PpWRGR GHFUHVFH j PHGLGD TXH FUHVFH R SHVR PROHFXODU GR SROtPHUR $OpP GLVWR
UHDo}HV ODWHUDLV GXUDQWH D SROLPHUL]DomR WDLV FRPR FLFOL]DomR UDPLILFDo}HV HWF
FRQGX]HPDYDORUHVGH M n GLIHUHQWHVGRUHDO$FLFOL]DomRSRUH[HPSORRFDVLRQD
XP GHFUpVFLPR QR Q~PHUR GH HTXLYDOHQWHV GH JUXSRV IXQFLRQDLV UHVXOWDQGR HP
YDORUHV GH M n  DFLPD GR HVSHUDGR 3RU RXWUR ODGR UDPLILFDo}HV FRQGX]HP D XP
DXPHQWR QR Q~PHUR GH HTXLYDOHQWHV GH JUXSRV IXQFLRQDLV XPD YH] TXH FDGD
UDPLILFDomR WHUPLQD FRP XP JUXSR IXQFLRQDO HP TXHVWmR 1HVWH FDVR R M n  VHUi
PHQRU GR TXH R HVSHUDGR (VWDV OLPLWDo}HV ID]HP FRP TXH WpFQLFDV EDVHDGDV QDV
SURSULHGDGHVFROLJDWLYDVVHMDPPDLVLQGLFDGDVSDUDDGHWHUPLQDomRGH M n 

4.2 Propriedades Coligativas


3URSULHGDGHVGHVROXo}HVWDLVFRPRDEDL[DPHQWRGDSUHVVmRGHYDSRUHOHYDomRGR
SRQWR GH HEXOLomR GHFUpVFLPR GR SRQWR GH FRQJHODPHQWR H SUHVVmR RVPyWLFD VmR
GHQRPLQDGDVSURSULHGDGHVFROLJDWLYDV
(VWDV SURSULHGDGHV EDVHLDPVH QR IDWR GH TXH D DGLomR GH XP VROXWR HP XP
VROYHQWHUHVXOWDHPXPDPXGDQoDPHQVXUiYHOQRSRWHQFLDOTXtPLFRGRVROYHQWH$
PXGDQoDQRSRWHQFLDOTXtPLFRHPWHUPRVGHDWLYLGDGHGRVROYHQWHpGHILQLGDFRPR

1 10 = RTlna1 (4.1)

RQGH 1 pRSRWHQFLDOTXtPLFRGRVROYHQWHQDVROXomR 1o pRSRWHQFLDOTXtPLFRGR


VROYHQWH SXUR QD PHVPD WHPSHUDWXUD H SUHVVmR a1  p D DWLYLGDGH GR VROYHQWH QD
VROXomR5pDFRQVWDQWHGRVJDVHVH7pDWHPSHUDWXUDDEVROXWD
(PXPVLVWHPDRQGHDVROXomRHVWiHPFRQWDWRFRPRVROYHQWHSXURSDUDTXHVH
DWLQMDRHTXLOtEULRpQHFHVViULRTXHRVSRWHQFLDLVTXtPLFRVGRVROYHQWHHGDVROXomR
VHMDPLJXDLV 1   1o ,VWRpDOFDQoDGRDWUDYpVGHPXGDQoDVQDWHPSHUDWXUDRX
SUHVVmRGDVROXomR(VWDVPXGDQoDVFRQVWLWXHPXPDPHGLGDGLUHWDGDDWLYLGDGHGR
VROYHQWH QD VROXomR H IRUPD D EDVH GRV PpWRGRV FROLJDWLYRV SDUD HVWXGRV GH
VROXo}HVGLOXtGDV
$ GHWHUPLQDomR GR SHVR PROHFXODU XWLOL]DQGR DV SURSULHGDGHV FROLJDWLYDV p
SRVVtYHO SRUTXH D DWLYLGDGH GR VROXWR HP VROXo}HV LQILQLWDPHQWH GLOXtGDV SRGH VHU

&DUDFWHUL]DomRGH3ROtPHURV 
FRQVLGHUDGD LJXDO j VXD IUDomR PRODU 'HVWD IRUPD D DWLYLGDGH GR VROYHQWH QD
VROXomRH[SUHVVDQD(TXDomRSRGHVHUVXEVWLWXtGDSHODVXDIUDomRPRODU x1 HD
YDULDomRGRSRWHQFLDOTXtPLFRSRGHHQWmRVHUH[SUHVVDSHOD(TXDomR

1 10 = RT ln x1 (4.2)

4XDQGR D VROXomR p PXLWR GLOXtGD HOD WHQGH D DSUHVHQWDU XP FRPSRUWDPHQWR


LGHDO3DUDHVWDVVROXo}HVRYDORUGDIUDomRPRODUGRVROYHQWHWHQGHDXP x1 1 H
RGDIUDomRPRODUGRVROXWRWHQGHD]HUR x2 0 
6DEHQGRVHTXH x1 = 1 x2 HQWmR ln x1 = ln (1 x2 )
([SDQGLQGR R WHUPR ln (1 x2 )  HP XPD VpULH H FRQVLGHUDQGR DSHQDV RV GRLV
SULPHLURVWHUPRVWHPRV

( )
OQ [ = OQ (  [  ) = [   [  

(4.3)

6XEVWLWXLQGRRWHUPR ln x1 GD(TXDomRSHOD(TXDomRWHPRV

[
 R = 57 [   (  )[ 
  ] (4.4)

6DEHVH TXH D IUDomR PRODU GH XP FRPSRQHQWH SRU H[HPSOR R VROXWR  HP XPD
VROXomR p LJXDO D UD]mR HQWUH R Q~PHUR GH PROHV GHVVH FRPSRQHQWH VROXWR  QD
VROXomR n2 HDVRPDGRQ~PHURGHPROHVGHFDGDFRPSRQHQWH (TXDomR 
Q
[ = (4.5)
Q + Q

3DUD VROXo}HV PXLWR GLOXtGDV (n1 + n2 )  p SUDWLFDPHQWH LJXDO D n1  Q~PHUR GH


PROHVGRVROYHQWH (QWmR

x2 = n2 (4.6)
n1
RQGH x1 pDIUDomRPRODUGRVROYHQWHQDVROXomRH n1 H n2 VmRUHVSHFWLYDPHQWHR
Q~PHURGHPROHVGRVROYHQWHHGRVROXWRQDVROXomR
3RURXWURODGRRYROXPHGDVROXomRSRGHVHUGHILQLGRFRPR
V = V1o n1 (4.7)

RQGH9pRYROXPHGDVROXomR9RpRYROXPHSDUFLDOPRODUGRVROYHQWHQDVROXomRH
QpRQ~PHURGHPROHVGRVROYHQWHQDVROXomR

 7pFQLFDVSDUD'HWHUPLQDomRGH3HVR0ROHFXODU1XPpULFR0pGLR
6DEHVHDLQGDTXHRQ~PHURGHPROHVpLJXDOjUD]mRHQWUHDPDVVDHPJUDPD
HRSHVRPROHFXODU (TXDomR 

n2 = m (4.8)
M
RQGHPpDPDVVDGRVROXWR SROtPHUR HPJUDPDVH0pRVHXSHVRPROHFXODU
&RPELQDQGR DV (TXDo}HV   H  D IUDomR PRODU GR VROXWR SROtPHUR  QD
VROXomRSRGHVHUGHILQLGDFRPR
P R
0 = P 9
[ = (4.9)
9 9 0
R9

&RPRDUD]mRP9pDFRQFHQWUDomRGRSROtPHURFHPJP/DIUDomRPRODU[
SRGHVHUUHHVFULWDFRPR
F  9 R
[ = (4.10)
0
$UHODomRHQWUHRSRWHQFLDOTXtPLFRGDPLVWXUDHDIUDomRPRODUGRSROtPHURQD
VROXomR (TXDomR SRGHHQWmRVHUHVFULWDFRPR

c 2V10
2

c V 0 M
1 1 = RT
0 2 1
+ +  (4.11)
M 2


RX

1
1 10 = RTc 2V10 + Ac 2 + Bc 22 +  (4.12)
M
RQGH0$H%VmRGHILQLGRVUHVSHFWLYDPHQWHFRPRRSULPHLURFRHILFLHQWHYLULDOR
VHJXQGRFRHILFLHQWHYLULDOHRWHUFHLURFRHILFLHQWHYLULDO
2SULPHLURFRHILFLHQWHYLULDOFRUUHVSRQGHDRLQYHUVRGRSHVRPROHFXODUQXPpULFR
PpGLR2VHJXQGRFRHILFLHQWHYLULDOHRWHUFHLURFRHILFLHQWHYLULDOIRUQHFHPXPDLGpLD
GDVLQWHUDo}HVHQWUHSROtPHURHVROYHQWHFRPRVHUiGLVFXWLGRSRVWHULRUPHQWH

&DUDFWHUL]DomRGH3ROtPHURV 
4XDQGR R SURFHVVR GH GLVVROXomR DWLQJH DV FRQGLo}HV GH HTXLOtEULR R SRWHQFLDO
TXtPLFRGDVROXomRVHLJXDODDRSRWHQFLDOTXtPLFRGRVROYHQWHSXUR R3DUD
TXHLVWRRFRUUDDWHPSHUDWXUDRXDSUHVVmRGRVLVWHPDpYDULDGD
(TXDo}HV SUiWLFDV TXH SHUPLWHP TXH VHMD FDOFXODGR R SHVR PROHFXODU QXPpULFR
PpGLRDSDUWLUGHSURSULHGDGHVFROLJDWLYDVVmRGDGDVDVHJXLU

S3DUDRVPRPHWULDGHPHPEUDQD

RT
lim = (4.13)
c o c Mn
RQGHpDSUHVVmRRVPyWLFDHFpDFRQFHQWUDomRGRSROtPHUR
S3DUDRVPRPHWULDGHSUHVVmRGHYDSRU

S 3 9 R
OLP = (4.14)
F R F 0Q
RQGH SpDGLIHUHQoDGHSUHVVmRGHYDSRUHQWUHVROYHQWHHVROXomR 3  pDSUHVVmR
R
GHYDSRUGRVROYHQWHSXURH9 pRYROXPHPRODUGRVROYHQWH

S3DUDFULRVFRSLD

T f RT f M s 1
2

lim =
c 0 H M (4.15)
c f n

RQGH 7IpRDEDL[DPHQWRGRSRQWRGHFRQJHODPHQWR pDGHQVLGDGHGRVROYHQWH


0VpRSHVRPROHFXODUGRVROYHQWH7IpRSRQWRGHFRQJHODPHQWRGRVROYHQWHH+Ip
DYDUDLomRGDHQWDOSLDGHIXVmR

S3DUDHEXOLRVFRSLD

T b RT b M s 1
2

lim =
(4.16)
c o c H b M n
RQGH 7EpDHOHYDomRGRSRQWRGHHEXOLomR7EpRSRQWRGHHEXOLomRGRVROYHQWHH
+EpDYDULDomRGDHQWDOSLDGHYDSRUL]DomR
2 HIHLWR GD DGLomR GH SROtPHURV GH SHVR PROHFXODU YDULDGR QDV SURSULHGDGHV
FROLJDWLYDV p LOXVWUDGR QD 7DEHOD  (VWH HIHLWR p PDLV SURQXQFLDGR QD SUHVVmR

 7pFQLFDVSDUD'HWHUPLQDomRGH3HVR0ROHFXODU1XPpULFR0pGLR
RVPyWLFDHSRULVVRHVWHpRPpWRGRFROLJDWLYRPDLVXWLOL]DGRSDUDGHWHUPLQDomRGR
SHVRPROHFXODUGHYLGRjUHODWLYDIDFLOLGDGHGDPHGLGD
&RPR DSUHVHQWDGR QD 7DEHOD  D PXGDQoD REVHUYDGD QD SUHVVmR GH YDSRU p
PXLWR SHTXHQD H SRU LVWR QmR SRGH VHU PHGLGD GLUHWDPHQWH FRP SUHFLVmR
(QWUHWDQWR RV HTXLSDPHQWRV XWLOL]DP PpWRGRV LQGLUHWRV SDUD D GHWHUPLQDomR GR
DEDL[DPHQWR GD SUHVVmR GH YDSRU GD VROXomR H WrP WLGR PXLWR VXFHVVR SDUD D
GHWHUPLQDomRGRSHVRPROHFXODUQXPpULFRPpGLRGHSROtPHURVFRPSHVRPROHFXODU
DWpFHUFDGH
'HYLGR j SRSXODULGDGH GRV PpWRGRV TXH HQYROYHP SUHVVmR GH YDSRU H SUHVVmR
RVPyWLFD DV WpFQLFDV GH FULRVFRSLD H HEXOLRVFRSLD QmR IRUDP PXLWR GHVHQYROYLGDV
SDUDSROtPHURV
7DEHOD&RPSDUDomRHQWUHDVVHQVLELOLGDGHVGRVYiULRVPpWRGRVFROLJDWLYRVSDUDGHWHUPLQDomRGRSHVR
PROHFXODU

6HQVLELOLGDGH
3URSULHGDGH
0 Q  0 Q  0 Q 
3UHVVmRRVPyWLFD FPGHVROYHQWH    
$EDL[DPHQWRGDSUHVVmRGHYDSRU
[ [ [
PP+J 
'HFUpVFLPRGRSRQWRGH
[ [ [
FRQJHODPHQWR R& 
(OHYDomRGRSRQWRGHHEXOLomR R&  [ [ [

4.2.1 Osmometria de presso de vapor


1RHVWDGRGHHTXLOtEULRKiVHPSUHYDSRUGRVFRPSRQHQWHVVREUHDVROXomROtTXLGD
&RPR GLVFXWLGR DQWHULRUPHQWH XPD PDFURPROpFXOD QmR FRQVHJXH SDVVDU SDUD R
HVWDGRGHYDSRUGHYLGRDRVHXDOWRSHVRPROHFXODU/RJRDSUHVVmRSDUFLDOGHYDSRU
GD PDFURPROpFXOD p FRQVLGHUDGD LJXDO D ]HUR S    $ SUHVVmR GH YDSRU TXH VH
PHGHpSRUWDQWRDSUHVVmRGHYDSRUGRFRPSRQHQWHGHEDL[RSHVRPROHFXODUVREUH
DVROXomRRXVHMDGRVROYHQWH$SUHVVmRGHYDSRUGRVROYHQWHVREUHDVROXomR S p
VHPSUHPHQRUGRTXHDSUHVVmRGHYDSRUGRVROYHQWHVREUHRVROYHQWHSXUR SR 
4XDQWRPDLRUIRUDFRQFHQWUDomRGRSROtPHURPHQRUVHUiDSUHVVmRGHYDSRUGR
VROYHQWH QD VROXomR H PDLRU VHUi HQWmR D GLIHUHQoD HQWUH S H SR $ PDLRULD GDV
VROXo}HV GH SROtPHURV DSUHVHQWD XP GHVYLR QHJDWLYR DFHQWXDGR GD LGHDOLGDGH $
)LJXUDLOXVWUDHVWHFRPSRUWDPHQWRRQGH[H[VmRUHVSHFWLYDPHQWHDVIUDo}HV
PRODUHV GR VROYHQWH H GR SROtPHUR QD VROXomR 3RGHVH REVHUYDU TXH PHVPR SDUD

&DUDFWHUL]DomRGH3ROtPHURV 
VROXo}HVUD]RDYHOPHQWHGLOXtGDVRGHVYLRMipDFHQWXDGR'HVWDIRUPDSDUDTXHDV
HTXDo}HVTXHUHODFLRQDPDYDULDomRGDSUHVVmRGHYDSRUFRPRSHVRPROHFXODUGR
SROtPHUR SRVVDP VHU XWLOL]DGDV p QHFHVViULR TXH VH WUDEDOKH FRP VROXo}HV EHP
GLOXtGDV GH SROtPHURV 3RU RXWUR ODGR HP VROXo}HV GLOXtGDV D GLIHUHQoD HQWUH DV
SUHVV}HVGHYDSRUSHSRpWmRSHTXHQDTXHFKHJDDVHULPHQVXUiYHO

)LJXUD'HSHQGrQFLDGDSUHVVmRGHYDSRUGRVROYHQWHVREUHDVROXomRGHSROtPHURHPUHODomRjIUDomR
PRODUGRVFRPSRQHQWHV

&RPRSRGHUtDPRVHQWmRGHWHUPLQDUHVWDGLIHUHQoDHUHODFLRQDUPRVFRPRSHVR
PROHFXODUGRSROtPHURTXHHVWiVHQGRDQDOLVDGR"
$ UHVSRVWD p TXH RV HTXLSDPHQWRV GLVSRQtYHLV QmR PHGHP GLUHWDPHQWH R
DEDL[DPHQWR GD SUHVVmR GH YDSRU GD VROXomR 1D YHUGDGH HVWHV HTXLSDPHQWRV
XWLOL]DPDYDULDomRGDWHPSHUDWXUDTXHDFRPSDQKDDYDULDomRGDSUHVVmRGHYDSRU
&RPR D WpFQLFD XWLOL]D VROXo}HV PXLWR GLOXtGDV SRGHPRV FRQVLGHUiODV FRPR
VROXo}HV SUDWLFDPHQWH LGHDLV 3RUWDQWR D OHL  GH 5DRXOW (TXDomR   SRGH VHU
HPSUHJDGD
p 1 = p1 o . x 1 (4.17)

RQGH S p D  SUHVVmR GH YDSRU GR VROYHQWH QD VROXomR SR p D SUHVVmR GH YDSRU GR
VROYHQWHSXURH[pDIUDomRPRODUGRVROYHQWHQDVROXomR
6DEHVHTXH
x1 = 1 - x2 (4.18)

 7pFQLFDVSDUD'HWHUPLQDomRGH3HVR0ROHFXODU1XPpULFR0pGLR
(QWmR
p1 = p1o (1-x2) (4.19)

p 1o - p 1 = p 1o.x 2 ou p = p1o.x2 (4.20)

$ GLIHUHQoD GH SUHVVmR GH YDSRU p UHODFLRQDGD FRP D GLIHUHQoD GH WHPSHUDWXUD
DWUDYpVGDHTXDomRGH&ODXVLXV&ODSH\URQGHVFULWDDVHJXLU
S S+Y
= (4.21)
7 57 
RQGH bS H b7 VmR UHVSHFWLYDPHQWH DV YDULDo}HV GH SUHVVmR GH YDSRU H GH
WHPSHUDWXUD +Y p D YDULDomR GD HQWDOSLD GH YDSRUL]DomR 7 p D WHPSHUDWXUD
DEVROXWDH5pDFRQVWDQWHGRVJDVHV
3DUD SHTXHQDV YDULDo}HV GH WHPSHUDWXUD 7  +Y H S SRGHP VHU FRQVLGHUDGRV
FRQVWDQWHV(QWmRD(TXDomRSRGHVHUGHVFULWDGDVHJXLQWHIRUPD

57 
7 = S (4.22)
S+Y
&RQVLGHUDQGRD(TXDomRHDVVXPLQGRTXHSDUDSHTXHQDVYDULDo}HVGHSD
SUHVVmR GH YDSRU GR VROYHQWH SXUR p SUDWLFDPHQWH LJXDO j SUHVVmR GH YDSRU GR
VROYHQWH QD VROXomR SR  S  D YDULDomR GD WHPSHUDWXUD SRGH VHU UHODFLRQDGD j
IUDomRPRODUGRSROtPHURQDVROXomRGHDFRUGRFRPD(TXDomR

57 
7 = [ (4.23)
+Y
/HPEUDQGRTXHDIUDomRPRODU[pLJXDODUD]mRHQWUHRQ~PHURGHPROHVGR
VROXWR  HGRVROYHQWH  QQHTXHRQ~PHURGHPROHVpGHILQLGRFRPRDUD]mR
HQWUHDPDVVDHPJUDPDVHRSHVRPROHFXODUDYDULDomRGDWHPSHUDWXUDSRGHVHU
H[SUHVVDGDVHJXLQWHIRUPD

57  Q 57  P 0
7 = =  (4.24)
+Y Q +Y 0  
RQGH P p D PDVVD HP JUDPD GR SROtPHUR $ UD]mR P p D FRQFHQWUDomR GR
SROtPHURQDVROXomRFH[SUHVVDHPJJ$YDULDomRGDWHPSHUDWXUDSRGHHQWmR

&DUDFWHUL]DomRGH3ROtPHURV 
VHU UHODFLRQDGD j FRQFHQWUDomR GD DPRVWUD H DR VHX SHVR PROHFXODU DWUDYpV GD
VHJXLQWHHTXDomR

57  F
7 = 0  (4.25)
+ Y 0
RXVLPSOHVPHQWH

c2
T = K (4.26)
M2

Descrio da tcnica
$)LJXUDLOXVWUDXPHVTXHPDGDFpOXODGHPHGLGDGHXPRVP{PHWURGHSUHVVmR
GH YDSRU WtSLFR $ FpOXOD FRQVLVWH GH XPD FkPDUD GH YLGUR   FRQWHQGR GRLV
WHUPLVWRUHVLJXDLVHVHQVtYHLVjWHPSHUDWXUD  $WHPSHUDWXUDGDFkPDUDGHYLGURp
FRQWURODGDDWUDYpVGHWHUPRVWDWRFRQVWLWXtGRGHXPEORFRGHDOXPtQLRDQRGL]DGR$
WHPSHUDWXUD GDV VHULQJDV DWUDYpV GDV TXDLV DV VROXo}HV VHUmR DGLFLRQDGDV QD
FkPDUDWDPEpPpFRQWURODGDDWUDYpVGHXPVHJXQGREORFRGHDTXHFLPHQWR  2V
WHUPLVWRUHV   VmR FRQHFWDGRV D XP FLUFXLWR HOpWULFR FDSD] GH PHGLU SHTXHQDV
GLIHUHQoDVGHWHPSHUDWXUDFRPDOWDSUHFLVmR
$ FkPDUD GH PHGLGD FRQWpP XPD SHTXHQD TXDQWLGDGH GR VROYHQWH H p
LQLFLDOPHQWHVDWXUDGDFRPYDSRUGHVWHVROYHQWHDXPDGHWHUPLQDGDWHPSHUDWXUD$
VROXomR D VHU DQDOLVDGD p FRORFDGD HP XPD GDV VHULQJDV HQTXDQWR TXH R VROYHQWH
SXURpFRORFDGRQDVHJXQGDVHULQJD(VWDVVHULQJDVVmRDUUDQMDGDVGHWDOIRUPDTXH
DVDJXOKDVHVWHMDPDOLQKDGDVDRVWHUPLVWRUHV

 7pFQLFDVSDUD'HWHUPLQDomRGH3HVR0ROHFXODU1XPpULFR0pGLR
)LJXUD(VTXHPDGDFpOXODGHPHGLGDGHXPRVP{PHWURGHSUHVVmRGHYDSRU

6H IRUHP FRORFDGDV JRWDV GR VROYHQWH SXUR HP DPERV RV WHUPLVWRUHV HVWHV
WHUPLVWRUHVHVWDUmRQDPHVPDWHPSHUDWXUD
$DGLomRGHXPDJRWDGHVROYHQWHSXURHPXPGRVWHUPLVWRUHVHGHXPDJRWDGD
VROXomRGLOXtGDGHSROtPHURQRRXWURWHUPLVWRUJHUDXPDGLIHUHQoDGHWHPSHUDWXUD
HQWUH HOHV 2 WHUPLVWRU FRQWHQGR D VROXomR WHUi LQLFLDOPHQWH XPD WHPSHUDWXUD
PHQRU GHYLGR j PHQRU SUHVVmR GH YDSRU 3DUD TXH VH UHVWDEHOHoD R HTXLOtEULR RX
VHMDSDUDTXH RRYDSRUGRVROYHQWHVLWXDGRQDFkPDUDGHYLGURVHFRQGHQVD
QD JRWD GD VROXomR (VWD FRQGHQVDomR SURYRFD XP DXPHQWR GD WHPSHUDWXUD GR
VROYHQWH GHYLGR j HYROXomR GR FDORU ODWHQWH GH YDSRUL]DomR $ FRQGHQVDomR H
FRQVHTXHQWHPHQWHRDXPHQWRGDWHPSHUDWXUDDFRQWHFHDWpTXHDSUHVVmRGHYDSRU
GD VROXomR FUHVoD H VH LJXDOH j SUHVVmR GH YDSRU GR VROYHQWH SXUR $ GLIHUHQoD GH
WHPSHUDWXUDPHGLGD 7pGLUHWDPHQWHSURSRUFLRQDODRDEDL[DPHQWRGDSUHVVmRGH
YDSRU H SRUWDQWR p UHODFLRQDGD DR SHVR PROHFXODU GR SROtPHUR $ GLIHUHQoD GH
WHPSHUDWXUDDXPHQWDFRPRDXPHQWRGDFRQFHQWUDomRGDVROXomRSROLPpULFD
&RPR RV WHUPLVWRUHV HVWmR FRQHFWDGRV D XP FLUFXLWR HOpWULFR R VLQDO UHJLVWUDGR
QRDSDUHOKRpQDYHUGDGHDGLIHUHQoDQDUHVLVWrQFLDHOpWULFD5DRLQYpVGH7

&DUDFWHUL]DomRGH3ROtPHURV 
3DUD D GHWHUPLQDomR GR SHVR PROHFXODU SUHSDUDPVH VROXo}HV GH SROtPHURV D
YiULDVFRQFHQWUDo}HV(VWDVFRQFHQWUDo}HVGHYHPHVWDUDEDL[RGHHPSHVR3DUD
FDGD FRQFHQWUDomR GHWHUPLQDVH D GLIHUHQoD GH WHPSHUDWXUD HQWUH RV WHUPLVWRUHV
RXPHOKRUDGLIHUHQoD5
$(TXDomRGHWUDEDOKRpVHPHOKDQWHj(TXDomRRXVHMD

c2 c22
R = K + 2 + (4.27)
2 M2 2
M
RX

R 1
= + A2 c2 + (4.28)
Kc2 M 2
&RORFDQGRVH HP JUiILFR 5.F YHUVXV F REWpPVH XPD UHWD $ H[WUDSRODomR j
FRQFHQWUDomR ]HUR FRHILFLHQWH OLQHDU  SHUPLWH D GHWHUPLQDomR GR SHVR PROHFXODU
QXPpULFRPpGLR2FRHILFLHQWHDQJXODUFRUUHVSRQGHDRVHJXQGRFRHILFLHQWHGRYLULDO
H IRUQHFH LQIRUPDo}HVVREUHDVLQWHUDo}HVHQWUHSROtPHURVROYHQWH(VWHJUiILFRp
LOXVWUDGRQD)LJXUDRQGH.pXPDFRQVWDQWHGHFDOLEUDomR
eLPSRUWDQWHHQIDWL]DUTXHTXDQWRPDLRUIRURYDORUGRFRHILFLHQWHDQJXODU $ 
PDLRUVHUiDLQWHUDomRSROtPHURVROYHQWH4XDQGRRVHJXQGRFRHILFLHQWHYLULDOIRU
LJXDOD]HURDVROXomRpGLWDLGHDORXVHMDQmRH[LVWHLQWHUDomRSUHIHUHQFLDOHQWUHRV
FRPSRQHQWHVGDVROXomR

 7pFQLFDVSDUD'HWHUPLQDomRGH3HVR0ROHFXODU1XPpULFR0pGLR
)LJXUD'HSHQGrQFLDGH5FYHUVXVFREWLGDDSDUWLUGHWpFQLFDGHRVPRPHWULDGHSUHVVmRGHYDSRU

Aspectos prticos
eLPSRUWDQWHHQIDWL]DUTXHSDUDTXHD(TXDomRVHMDYiOLGDQmRSRGHUiKDYHU
SHUGD DOJXPD GH FDORU SRU FRQGHQVDomR RX UDGLDomR D VDWXUDomR GR YDSRU QD
FkPDUD GHYH VHU FRPSOHWD H D FRQGHQVDomR QD VXSHUItFLH GR OtTXLGR GHYH VHU
HILFLHQWH 7DLV FRQGLo}HV VmR LPSRVVtYHLV GH VHUHP DOFDQoDGDV QD SUiWLFD 'HVWD
IRUPD p QHFHVViULR ID]HU D FDOLEUDomR GR HTXLSDPHQWR FRP VXEVWkQFLDV GH SHVR
PROHFXODU FRQKHFLGR  $ 7DEHOD  DSUHVHQWD DOJXQV H[HPSORV GH VXEVWkQFLDV
FRPXPHQWH XVDGDV SDUD FDOLEUDomR 2V SDGU}HV PDLV XVDGRV VmR RV GH EDL[R SHVR
PROHFXODU 3DGU}HV GH SROLHVWLUHQR FRP GLVWULEXLomR HVWUHLWD GH SHVR PROHFXODU
WDPEpPVmRXWLOL]DGRVHPERUDHOHVQmRSRVVDPVHUFRQVLGHUDGRVVXEVWkQFLDVSXUDV
XPDYH]TXHHOHVSRVVXHPXPDSROLGLVSHUVmRPXLWRSUy[LPDPDVQmRLJXDODXP
(P FHUWRV FDVRV D XWLOL]DomR GH SDGU}HV GH SROLHVWLUHQR p ~WLO SRUTXH FHUWRV
HTXLSDPHQWRV QHFHVVLWDP GH FDOLEUDomR FRP PDWHULDLV GH SHVR PROHFXODU SUy[LPR
DRGRSROtPHURDVHUDQDOLVDGR
$ VHOHomR GR VROYHQWH H GD WHPSHUDWXUD p WDPEpP PXLWR LPSRUWDQWH SDUD R
VXFHVVRGDVH[SHULrQFLDVHQYROYHQGRRVPRPHWULDGHSUHVVmRGHYDSRU3UDWLFDPHQWH
WRGRVRVVROYHQWHVFRPXQVLQFOXLQGRiJXDSRGHPVHUXVDGRVQDWpFQLFDGH932$
WHPSHUDWXUDGHYHVHUHVFROKLGDGHWDOIRUPDTXHDSUHVVmRGHYDSRUGRVROYHQWHVHMD
PDLRUGRTXHWRUUSRUpPQmRGHYHVHUH[FHVVLYDPHQWHDOWDSDUDQmRRFDVLRQDU
SUREOHPDVFRPHYDSRUDomRQDFkPDUDGR932
3DUDILQDOL]DURPpWRGRIXQFLRQDPXLWREHPSDUDPHGLGDVGH M QFXMRVYDORUHV
HQFRQWUHPVHDEDL[RGH

&DUDFWHUL]DomRGH3ROtPHURV 
7DEHOD3DGU}HVFRPXQVSDUDFDOLEUDomRGHRVP{PHWURGHSUHVVmRGHYDSRU

3DGUmR 6ROXELOLGDGH
0DQLWRO JXD
6XFURVH JXD
%HQ]LOD 6ROYHQWHRUJkQLFR
%LIHQLOD 6ROYHQWHRUJkQLFR
3DGU}HVGHSROLHVWLUHQR 6ROYHQWHRUJkQLFR

$QWHVGDDQiOLVHGDVXEVWkQFLDSURSULDPHQWHGLWDGHYHVHSURFHGHUjFDOLEUDomR
GRDSDUHOKRGHWHUPLQDQGRVHDFRQVWDQWH.HRHUURGDPHGLGD
3DUDGHWHUPLQDomRGDFRQVWDQWH.GRDSDUHOKRGHYHPVHID]HUDVPHGLGDVGH5
GDVXEVWkQFLDXVDGDFRPRSDGUmRGHFDOLEUDomR EHQ]LODSRUH[HPSOR XWLOL]DQGRVH
VROXo}HVDYiULDVFRQFHQWUDo}HV(PVHJXLGDWUDoDVHXPJUiILFRGH 5FYHUVXVFH
H[WUDSRODVH D FRQFHQWUDomR ]HUR $ FRQVWDQWH GR DSDUHOKR VHUi REWLGD DWUDYpV GD
VHJXLQWHHTXDomR

K = PM x (R/c)c0 (4.29)

RQGH30pRSHVRPROHFXODUGDEHQ]LOD 
3DUD GHWHUPLQDomR GR HUUR GR DSDUHOKR UHDOL]DVH R PHVPR SURFHGLPHQWR
DQWHULRU XWLOL]DQGR XP RXWUR SDGUmR SRU H[HPSOR LVRFWDQR  1HVWH FDVR WDPEpP
VmRXWLOL]DGDVVROXo}HVDYiULDVFRQFHQWUDo}HV&RORFDVHHPJUiILFR 5FYHUVXVFH
H[WUDSRODVH D FRQFHQWUDomR ]HUR 'HWHUPLQDVH R YDORU GR SHVR PROHFXODU GR
LVRFWDQR XWLOL]DQGR D (TXDomR  H R YDORU GH . REWLGR QD H[SHULrQFLD FRP D
EHQ]LOD
2HUURGRDSDUHOKRVHUiGHWHUPLQDGRFRPSDUDQGRRYDORUUHDOGRSHVRPROHFXODU
GRLVRFWDQR  HRYDORUHQFRQWUDGRQDPHGLGD


4.2.2 Osmometria de membrana


2VPRVH p R IHQ{PHQR GH SDVVDJHP GH XP VROYHQWH SDUD XPD VROXomR DWUDYpV GH
XPD PHPEUDQD VHPLSHUPHiYHO RX VHMD XPD PHPEUDQD SHUPHiYHO Vy SDUD
PROpFXODV GH VROYHQWH SRUpP LPSHUPHiYHO SDUD PROpFXODV GR VROXWR 3DUD TXH D
PHPEUDQD VHMD LPSHUPHiYHO R WDPDQKR GRV SRURV GD PHPEUDQD GHYH VHU PHQRU
GRTXHRWDPDQKRGDVPROpFXODVGRVROXWRFRPRpRFDVRGDVPDFURPROpFXODV
2 SRWHQFLDO TXtPLFR GH XP VROYHQWH QD VROXomR p VHPSUH PHQRU GR TXH R
SRWHQFLDO TXtPLFR GR VROYHQWH SXUR  < R  6H D VROXomR H R VROYHQWH IRUHP
VHSDUDGRVSRUXPDPHPEUDQDVHPLSHUPHiYHOKDYHUiXPDWHQGrQFLDGDVPROpFXODV
GR VROYHQWH QR FRPSDUWLPHQWR GR VROYHQWH SXUR HP IOXLU DWUDYpV GD PHPEUDQD

 7pFQLFDVSDUD'HWHUPLQDomRGH3HVR0ROHFXODU1XPpULFR0pGLR
SDVVDQGR SDUD D VROXomR (VWH IHQ{PHQR RFRUUH DWp TXH RV SRWHQFLDLV TXtPLFRV GH
DPERVRVODGRVVHLJXDOHPRXVHMDDWpTXHVHHVWDEHOHoDRHTXLOtEULR
$ )LJXUD  DSUHVHQWD XP HVTXHPD GR IHQ{PHQR TXH RFRUUH TXDQGR VROYHQWH
SXURHVROXomRVmRVHSDUDGRVSRUXPDPHPEUDQDVHPLSHUPHiYHO2FRPSDUWLPHQWR
jGLUHLWDFRQWpPRVROYHQWHSXURHRFRPSDUWLPHQWRjHVTXHUGDFRQWpPDVROXomR2
YROXPH GH DPERV RV FRPSRQHQWHV p VHSDUDGR SHOD PHPEUDQD VHPLSHUPHiYHO 1R
LQtFLR GR SURFHVVR )LJXUD D RVYROXPHVVmRLJXDLVSRUpPRSRWHQFLDOTXtPLFR
GRFRPSDUWLPHQWRjGLUHLWD VROYHQWHSXUR pPDLRUGRTXHDTXHOHGDHVTXHUGD6HD
SUHVVmR H[WHUQD HP DPERV RV ODGRV IRU D PHVPD R VROYHQWH SDVVDUi SDUD R ODGR
HVTXHUGR SDUD HTXLOLEUDU RV SRWHQFLDLV TXtPLFRV &RP LVWR R YROXPH GR
FRPSDUWLPHQWRjHVTXHUGDDXPHQWDUi )LJXUDE 
6HIRUDSOLFDGDXPDSUHVVmRQRFRPSDUWLPHQWRGDVROXomRSDUDHYLWDUTXDOTXHU
YDULDomR GH YROXPH HVWDEHOHFHUVHi XP HTXLOtEULR GLQkPLFR RQGH   R
&RQVLGHUDQGR SR D SUHVVmR H[WHUQD VREUH R VROYHQWH SXUR H S D SUHVVmR VREUH D
VROXomR D GLIHUHQoD GH SUHVVmR QR PRPHQWR GR HTXLOtEULR p LJXDO j SUHVVmR
RVPyWLFD

= p - po (4.30)
RQGHSpDSUHVVmRDVHUH[HUFLGDVREUHDVROXomRSDUDTXHRSRWHQFLDOTXtPLFRGD
VROXomR  VH WRUQH LJXDO DR SRWHQFLDO TXtPLFR GR VROYHQWH SXUR  (P RXWUDV
SDODYUDVDSUHVVmRRVPyWLFDGHXPDVROXomRpDSUHVVmRTXHSUHFLVDVHUDSOLFDGDj
VROXomRGHIRUPDDLJXDODUDDWLYLGDGHGRVROYHQWHFRPDDWLYLGDGHGDVROXomR


)LJXUD5HSUHVHQWDomRHVTXHPiWLFDGRSURFHVVRGHRVPRVHDWUDYpVGHXPDPHPEUDQDVHPLSHUPHiYHO

2EVHUYDQGRD)LJXUDEDSUHVVmRRVPyWLFD pLQGLFDGDSHODGLIHUHQoDHQWUH
DVDOWXUDVGRVOtTXLGRVKQRVEUDoRVODWHUDLVGRFRPSDUWLPHQWR

&DUDFWHUL]DomRGH3ROtPHURV 
$YDULDomRGRSRWHQFLDOTXtPLFRFRPDSUHVVmRjWHPSHUDWXUDFRQVWDQWHpGDGD
SHODVHJXLQWHHTXDomR


= V1 (4.31)
p T
RX
= V1p (4.32)
,QWHJUDQGRWHUHPRV

1
o
p

1 = V P 1 (4.33)
1 p o

1RVH[SHULPHQWRVUHODFLRQDGRVjRVPRPHWULDGHPHPEUDQDRYROXPHpVHPSUH
PDQWLGRFRQVWDQWH(QWmR

1o - 1 = V1o(p po) = V1 (4.34)


R
RQGHpDSUHVVmRRVPyWLFDH9 pRYROXPHSDUFLDOPRODUGRVROYHQWHSXUR

&RPELQDQGRVHD(TXDomRFRPD(TXDomRWHPVHTXH

1 - 1o = 1 = RTlnx1 = - V1o (4.35)


RX

RT
= O ln x 1 (4.36)
V1
RQGH5pDFRQVWDQWHGRVJDVHVSHUIHLWRVH7pDWHPSHUDWXUDDEVROXWD HP.HOYLQ 
&RPR
lnx1 = ln(1-x2) = -x2 x22/2 - .... (4.37)
HQWmR

RT
= O x2 (4.38)
V1
$IUDomRPRODUGRFRPSRQHQWHpLJXDOD

 7pFQLFDVSDUD'HWHUPLQDomRGH3HVR0ROHFXODU1XPpULFR0pGLR
n2
x2 =
n1 + n2
(4.39)

RQGHQHQVmRRVQ~PHURVGHPROHVGRVROYHQWHHGRSROtPHURUHVSHFWLYDPHQWH
3DUDVROXo}HVGLOXtGDVQQHSRUWDQWR[QQ
6XEVWLWXLQGR R WHUPR [ SHOR Q~PHUR GH PROHV GRV FRPSRQHQWHV QD (TXDomR
WHPRV

RT n 2
= (4.40)
V1O n1
2YROXPHSDUFLDOPRODUGRVROYHQWHSXUR9RPXOWLSOLFDGRSHORVHXQ~PHURGH
PROHVQpLJXDODRYROXPHGDVROXomR9
3RU RXWUR ODGR R Q~PHUR GH PROHV GH SROtPHUR Q GLYLGLGR SHOR YROXPH GD
VROXomRpLJXDOjFRQFHQWUDomRGHVROXWRQDVROXomRHPPROHVSRUOLWUR
$VVLPD(TXDomRSRGHVHUH[SUHVVDGDVHJXLQWHPDQHLUD

RT
= n 2 = c 2 RT (4.41)
V
$ (TXDomR  p FRQKHFLGD FRPR HTXDomR GH YDQW +RII (VWD HTXDomR QmR p
DGHTXDGD D VROXo}HV GH SROtPHURV PHVPR TXDQGR GLOXtGDV GHYLGR DRV IDWRUHV
UHODFLRQDGRVDLQWHUDo}HVSROtPHURVROYHQWH
3DUD VROXo}HV SROLPpULFDV p QHFHVViULR OHYDU HP FRQWD RV RXWURV WHUPRV GD
(TXDomRRXVHMD

57 Q
= Q
 + +  (4.42)
9 Q
6DEHQGRVHTXHRQ~PHURGHPROHVpLJXDOjPDVVDGDDPRVWUDHPJUDPDV Z 
GLYLGLGDSHORVHXSHVRPROHFXODU 0  Q Z0 HVDEHQGRVHWDPEpPTXHDPDVVD
GD DPRVWUD Z  GLYLGLGD SHOR YROXPH GD VROXomR 9  p LJXDO j FRQFHQWUDomR GR
SROtPHURQDVROXomRWHPRV


= 57F + $F  + $F  +  (4.43)
0Q




&DUDFWHUL]DomRGH3ROtPHURV 
RXUHDUUDQMDQGR


= 57 + $F  + $F  +  (4.44)
F 0Q
RQGHFpDFRQFHQWUDomRGRSROtPHURHPJP/ M n pRSHVRPROHFXODUQXPpULFR
PpGLR H $ H $ VmR UHVSHFWLYDPHQWH R VHJXQGR FRHILFLHQWH YLULDO H R WHUFHLUR
FRHILFLHQWHYLULDO2WHUPRFpGHQRPLQDGRSUHVVmRRVPyWLFDUHGX]LGD
&RORFDQGRVH HP JUiILFR F YHUVXV F REWpPVH XPD UHWD RQGH R FRHILFLHQWH
OLQHDUFRUUHVSRQGHDRLQYHUVRGH M n HRFRHILFLHQWHDQJXODUUHSUHVHQWDRVHJXQGR
FRHILFLHQWH YLULDO (VWH ~OWLPR QRV IRUQHFH LQIRUPDo}HV D UHVSHLWR GDV LQWHUDo}HV
SROtPHURVROYHQWH
$)LJXUDDSUHVHQWDDGHSHQGrQFLDGHFFRPDFRQFHQWUDomRGHVROXomRGH
SROtPHURHPGLIHUHQWHVVROYHQWHV7RGDVDVUHWDVHQFRQWUDPVHQRPHVPRSRQWR QD
RUGHQDGD  LQGLFDQGR TXH R YDORU REWLGR GH SHVR PROHFXODU QXPpULFR PpGLR
LQGHSHQGHGRWLSRGHVROYHQWH

)LJXUD'HSHQGrQFLDGHFFRPDFRQFHQWUDomRGHVROXomRGHSROtPHURHPGLIHUHQWHVVROYHQWHV 2
DXPHQWRGRFRHILFLHQWHDQJXODUVLJQLILFDDXPHQWRGDLQWHUDomRSROtPHURVROYHQWH 

2 FRHILFLHQWH DQJXODU HQWUHWDQWR YDULD FRP D QDWXUH]D GR VROYHQWH 4XDQWR


PDLRU IRU R YDORU GR FRHILFLHQWH DQJXODU $ PDLRU VHUi D LQWHUDomR SROtPHUR 
VROYHQWH ERQVVROYHQWHV 4XDQGRRFRHILFLHQWHDQJXODUIRULJXDOD]HURFRQVLGHUD
VH R VLVWHPD FRPR LGHDO RX VHMD QmR H[LVWH LQWHUDomR SUHIHUHQFLDO HQWUH RV
FRPSRQHQWHV GD VROXomR 9DORUHV GH $ PHQRUHV GR TXH ]HUR LQGLFDP PDXV
VROYHQWHV

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4XDQGRRVHJXQGRFRHILFLHQWHYLULDO$IRULJXDOD]HURRVLVWHPDpFRQVLGHUDGR
HVWDUVREFRQGLo}HVWHWD&RQGLo}HVWHWDVmRDTXHODVQmRSHUWXUEDGDVSRULQWHUDo}HV
SUHIHUHQFLDLVGHTXDLVTXHUFRPSRQHQWHV$FRQGLomRWHWDpDOFDQoDGDDXPVROYHQWH
H D XPD WHPSHUDWXUD GHILQLGRV 2 VROYHQWH H D WHPSHUDWXUD VmR HQWmR
GHQRPLQDGRVUHVSHFWLYDPHQWHVROYHQWHWHWDHWHPSHUDWXUDWHWD
$7DEHODLOXVWUDRVYDORUHVGRVHJXQGRFRHILFLHQWHYLULDOSDUDDOJXQVVLVWHPDV
SROtPHURVROYHQWH
7DEHOD9DORUHVGRVHJXQGRFRHILFLHQWHYLULDOSDUDDOJXQVSDUHVSROtPHURVROYHQWHDXPDGHWHUPLQDGD
WHPSHUDWXUD

7HPSHUDWXUD $[
3ROtPHUR 0 Q [ 6ROYHQWH
R&  FPPROJ 
3ROLHVWLUHQR  7ROXHQR  
3ROLHVWLUHQR  'LFORURHWDQR  
3ROLHVWLUHQR  &LFORKH[DQR  
3ROLLVREXWLOHQR  &LFORKH[DQR  
3ROLLVREXWLOHQR  %HQ]HQR  

3DUDXPGHWHUPLQDGRVROYHQWH H[FHWRHPFRQGLo}HVWHWD RYDORUGH$GHFUHVFH


FRP R DXPHQWR GR SHVR PROHFXODU GR SROtPHUR (VWH FRPSRUWDPHQWR p IiFLO GH
HQWHQGHUXPDYH]TXHFRPRDXPHQWRGDFDGHLDSROLPpULFDDVXDVROXELOLGDGHILFD
PDLV GLItFLO $ GHSHQGrQFLD GH $ FRP R SHVR PROHFXODU SRGH VHU HQFRQWUDGD
XWLOL]DQGRDUHODomRHPStULFD

A2 KM n (4.45)
RQGH . p XPD FRQVWDQWH HPStULFD H    SDUD SROtPHURV IOH[tYHLV HP ERQV
VROYHQWHV
2WHUPR$FGD(TXDomRpIUHTHQWHPHQWHLJQRUDGRSDUDDGHWHUPLQDomR
GDGHSHQGrQFLDGHFHPIXQomRGHFXPDYH]TXHDVPHGLGDVVmRUHDOL]DGDVHP
VROXo}HVPXLWRGLOXtGDVHSRULVWRRWHUPRFpGHVSUH]tYHO
(QWUHWDQWRTXDQGRVHWUDEDOKDFRPVROXo}HVXPSRXFRPDLVFRQFHQWUDGDVHVWH
WHUPR FRPHoD D LQIOXHQFLDU 1HVWH FDVR D GHSHQGrQFLD GH F YHUVXV F FRPHoD D
DSUHVHQWDU XPD FXUYDWXUD D FRQFHQWUDo}HV PDLV DOWDV 3DUD HOLPLQDU RX PLQLPL]DU
HVWD GLVFUHSkQFLD QR FRPSRUWDPHQWR FRVWXPDVH UHODFLRQDU F  YHUVXV F $
XWLOL]DomR GD UDL] TXDGUDGD p QRUPDOPHQWH UHFRPHQGDGD SDUD SROLPHURV GH DOWR
SHVR PROHFXODU $ )LJXUD  DSUHVHQWD D UHODomR GD SUHVVmR RVPyWLFD FRP D
FRQFHQWUDomR XWLOL]DQGRVH DV UHODo}HV F YHUVXV F H F  YHUVXV F 2EVHUYDVH
TXHQRVHJXQGRFDVRDGHSHQGrQFLDpOLQHDU

&DUDFWHUL]DomRGH3ROtPHURV 
)LJXUD'HSHQGrQFLDHQWUHDSUHVVmRRVPyWLFDHDFRQFHQWUDomRGHVROXomRGHSROLEXWDGLHQR
 0 Q   

Parte prtica
2V HTXLSDPHQWRV XWLOL]DGRV SDUD PHGLGDV GH SHVR PROHFXODU SRU HVWH PpWRGR VmR
FKDPDGRV RVP{PHWURV $V PHGLGDV SRGHP VHU UHDOL]DGDV SRU PpWRGR HVWiWLFR RX
GLQkPLFR 2 PpWRGR HVWiWLFR FRQVLVWH HP PHGLU D GLIHUHQoD GH QtYHO HQWUH RV GRLV
FRPSDUWLPHQWRV VROYHQWH H VROXomR  QR HTXLOtEULR (TXLSDPHQWRV TXH WUDEDOKDP
FRP HVWH PpWRGR SRVVXHP D YDQWDJHP GH WHU XP GHVLJQ PXLWR VLPSOHV
(QWUHWDQWRRHTXLOtEULRpDOFDQoDGRDWHPSRVPXLWRORQJRVRTXHLQGX]DHUURVGH
PHGLGD
2 PpWRGR GLQkPLFR p EDVHDGR QD PHGLGD GD YHORFLGDGH GR IOX[R GR VROYHQWH
DWUDYpVGDPHPEUDQDGHSHQGHQGRGDSUHVVmRDSOLFDGD
2V HTXLSDPHQWRV PDLV PRGHUQRV VmR DXWRPiWLFRV H RSHUDP XWLOL]DQGR
GLUHWDPHQWH XP WUDQVGXWRU GH SUHVVmR RX XP PHFDQLVPR GH FRQWUROH HOHWU{QLFR
VHUYRPHFDQLVPR  SDUD HTXLOLEUDU D SUHVVmR KLGURVWiWLFD H SUHYHQLU D GLIXVmR GR
VROYHQWHDWUDYpVGDPHPEUDQD

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$ )LJXUD  DSUHVHQWD R HVTXHPD GH XP RVP{PHWUR DXWRPiWLFR 1HVWHV
LQVWUXPHQWRV RV FRPSDUWLPHQWRV GR VROYHQWH H GD VROXomR VmR VHSDUDGRV SHOD
PHPEUDQD H R VLVWHPD p PDQWLGR IHFKDGR $ WHQGrQFLD GR VROYHQWH GH SDVVDU GR
FRPSDUWLPHQWR GR VROYHQWH SXUR SDUD R FRPSDUWLPHQWR GD VROXomR JHUD XPD
GHIRUPDomR GR GLDIUDJPD IOH[tYHO ORFDOL]DGR QR FRPSDUWLPHQWR GR VROYHQWH 8PD
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)LJXUD(VTXHPDGHXPRVP{PHWURDXWRPiWLFR

$ FRQILDELOLGDGH GDV PHGLGDV REWLGDV SRU RVPRPHWULD GHSHQGH IXQGDPHQ


WDOPHQWHGDTXDOLGDGHGDPHPEUDQD$PHPEUDQDGHYHVHUSHUPHiYHODRVROYHQWH
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FRQWDWR FRP R VROYHQWH $ PDLRULD GDV PHPEUDQDV p IHLWD j EDVH GH FHOXORVH
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FHOXORVHpUHFRPHQGDGRSDUDVROXo}HVDTXRVDV
7RGRV RV WLSRV GH PHPEUDQD GHYHP VHU FRQGLFLRQDGRV QR VROYHQWH GH DQiOLVH
DQWHVGHVHUHPXWLOL]DGRV1RFDVRGHPHPEUDQDVSUHYLDPHQWHHPEHELGDVHPiJXD
R FRQGLFLRQDPHQWR GHYH VHU IHLWR SULPHLUDPHQWH HP PHWDQRO RX DFHWRQD H
VXEVHTHQWHPHQWHQRVROYHQWHRUJkQLFRTXHVHUiXWLOL]DGRQRH[SHULPHQWR
3DUDDGHWHUPLQDomRGRSHVRPROHFXODUQXPpULFRPpGLRDVPHGLGDVGHYHPVHU
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5.1 Espalhamento de luz


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5.1.3 Princpio terico de espalhamento de luz


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5.1.4 Espalhamento de luz em soluo de partculas pequenas


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'H DFRUGR FRP R FRQFHLWR WHUPRGLQkPLFR FRQVLGHUDVH TXH DV IOXWXDo}HV QD
SRODUL]DELOLGDGH GDV PROpFXODV SRU FRQWDV GDV LQWHUDo}HV LQWHUPROHFXODUHV HP
WHPSHUDWXUDSUHVVmRHQ~PHURGHSDUWtFXODVHVSDOKDQWHVFRQVWDQWHV GHSHQGHPGR
SRWHQFLDOTXtPLFRHSRUWDQWRSRGHPVHUUHODFLRQDGDVjSUHVVmRRVPyWLFD
$VVLPDYDULDomRGDUD]mRGH5D\OHLJKGDVROXomRFRPUHODomRDRVROYHQWHSXUR
SRGHVHUH[SUHVVDSHODH[SDQVmRYLULDOVHJXQGRD(TXDomR

Kc 1
= + 2 A2 c + 3 A3c2 +......
R M (5.10)

RQGH $ H $ VmR FRQKHFLGRV UHVSHFWLYDPHQWH FRPR VHJXQGR FRHILFLHQWH YLULDO H
WHUFHLUR FRHILFLHQWH YLULDO H GHVFUHYHP DV PXGDQoDV QD SURSULHGDGH GH
HVSDOKDPHQWR FDXVDGDV SHODV LQWHUDo}HV LQWHUPROHFXODUHV D FRQFHQWUDo}HV ILQLWDV
1DPDLRULDGRVFDVRVRWHUFHLURWHUPRpPXLWRSHTXHQRHSRUWDQWRGHVSUH]DGR
&RPR GLVFXWLGR HP FDStWXORV DQWHULRUHV $ SRVLWLYR LQGLFD ERD LQWHUDomR
SROtPHURVROYHQWH HQTXDQWR TXH $ QHJDWLYR LQGLFD TXH DV LQWHUDo}HV SROtPHUR
SROtPHUR VmR PDLRUHV GR TXH DV LQWHUDo}HV SROtPHURVROYHQWH LVWR p R VROYHQWH
XWLOL]DGRpXPPDXVROYHQWHSDUDDPDFURPROpFXOD
5HVXPLQGR SDUD SDUWtFXODV PHQRUHV GR TXH  DV PHGLGDV GH HVSDOKDPHQWR
GHOX]SRGHPVHUIHLWDVDXPkQJXORIL[RQRUPDOPHQWHGH
3DUDGHWHUPLQDUDUD]mRGH5D\OHLJKGDVROXomRHGRVROYHQWHSXURUHODFLRQDVHD
LQWHQVLGDGHGDOX]HVSDOKDGDHPFDGDXPGRVPHLRVFRPDOX]LQFLGHQWH

Razo de Rayleigh da soluo:

I , sol
R , sol = .r 2 (5.11)
Io

&DUDFWHUL]DomRGH3ROtPHURV 
Razo de Rayleigh do solvente puro:

I , solvente
R , o = .r 2 (5.12)
Io
3DUD VH GHWHUPLQDU D LQWHQVLGDGH GD OX] LQFLGHQWH ,R XVDVH QRUPDOPHQWH XP
VROYHQWH SDGUmR GH UD]mR GH 5D\OHLJK FRQKHFLGD FRPR SRU H[HPSOR R EHQ]HQR
$VVLP

I , benzeno
R , benzeno = .r 2 (5.13)
Io
/RJR

I , sol . R , benzeno
R , sol = (5.14)
I , benzeno

I , solvente . R , benzeno
R ,o = (5.15)
I , benzeno
$ YDULDomR GD UD]mR GH 5D\OHLJK p FRORFDGD HP JUiILFR HP IXQomR GD
FRQFHQWUDomRREWHQGRVHDUHWDLOXVWUDGDQD)LJXUD$SDUWLUGRFRHILFLHQWHOLQHDU
GD UHWD REWpPVH R LQYHUVR GR SHVR PROHFXODU H D SDUWLU GR FRHILFLHQWH DQJXODU
REWpPVHRVHJXQGRFRHILFLHQWHYLULDO

 7pFQLFDSDUD'HWHUPLQDomRGH3HVR0ROHFXODU3RQGHUDO0pGLR
Figura 5.4. Dependncia da razo de Rayleigh com a concentrao de uma soluo de
partculas, cuja maior dimenso em soluo seja menor do que /20.

5.1.5 Espalhamento de luz em partculas grandes


$ (TXDomR  Vy p YiOLGD SDUD SDUWtFXODV SHTXHQDV 3DUD PDFURPROpFXODV FXMR
WDPDQKRGRQRYHORpPDLRUGRTXH DLQWHQVLGDGHGDOX]HVSDOKDGD , YDULD
FRP R kQJXOR GH REVHUYDomR ,VWR RFRUUH SRUTXH R HVSDOKDPHQWR SRGHUi RFRUUHU D
SDUWLU GH YiULRV FHQWURV GD PHVPD SDUWtFXOD (VWH HVSDOKDPHQWR H[LELUi XPD
GLIHUHQoD GH IDVH GH DFRUGR FRP R kQJXOR HQWUH R REVHUYDGRU H D GLUHomR GD OX]
LQFLGHQWH $ )LJXUD  LOXVWUD D JHRPHWULD GD OX] HVSDOKDGD D SDUWLU GH GRLV
GLIHUHQWHVSRQWRV3H3GHXPDPHVPDPDFURPROpFXOD

)LJXUD*HRPHWULDGDOX]HVSDOKDGDDSDUWLUGHGRLVSRQWRV3H3GHXPDPHVPDPDFURPROpFXOD

&DUDFWHUL]DomRGH3ROtPHURV 
(VWD GLIHUHQoD GH IDVH p RULJLQDGD GD GLIHUHQoD HQWUH DV GLVWkQFLDV GRV FHQWURV
HVSDOKDQWHV3H3HRREVHUYDGRU$XPkQJXOR]HURRXVHMDTXDQGRRREVHUYDGRU
VHHQFRQWUDSUDWLFDPHQWHQDGLUHomRGDOX]LQFLGHQWHDGLIHUHQoDp]HURPHGLGD
TXHRkQJXORGHREVHUYDomRpDXPHQWDGRHVWDGLIHUHQoDDXPHQWD&RPRSRGHVHU
REVHUYDGR QD )LJXUD  TXDQGR R REVHUYDGRU HQFRQWUDVH D XP kQJXOR  D
GLIHUHQoDGHIDVHFRUUHVSRQGHD'4XDQGRRREVHUYDGRUHQFRQWUDVHDXPkQJXOR
 PDLRU GR TXH  D GLIHUHQoD GH IDVH ' p PDLRU (VWH DXPHQWR QD GLIHUHQoD GH
IDVHUHVXOWDHPXPGHFUpVFLPRQDLQWHQVLGDGHGDOX]HVSDOKDGD
&RQVLGHUDQGR HVWDV GLIHUHQoDV GH LQWHQVLGDGH GH OX] HVSDOKDGD p QHFHVViULR
LQWURGX]LUXPIDWRUGHHVSDOKDPHQWR3 DRVFiOFXORV
2 IDWRU GH HVSDOKDPHQWR RX IDWRU IRUPD p GHILQLGR FRPR D UD]mR HQWUH D
LQWHQVLGDGH GD OX] HVSDOKDGD PHGLGD D XP kQJXOR  5  H D LQWHQVLGDGH GD OX]
HVSDOKDGDH[WUDSRODGDDXPkQJXOR]HUR 5 
intensidade de luz espalhada a um ngulo finito R
P( ) = = (5.16)
intensidade da luz espalhada a um ngulo zero R0
(QWmR SDUD PDFURPROpFXODV DV H[SHULrQFLDV GH HVSDOKDPHQWRGHOX]HQYROYHP
H[WUDSRODo}HVDFRQFHQWUDomR]HURHDkQJXOR]HUR
3DUDTXDOTXHUPDFURPROpFXODGHTXDOTXHUIRUPDRXWDPDQKR3 VHUiVHPSUH
DXPkQJXOR]HURPHGLGDTXHRkQJXORGHREVHUYDomRFUHVFHRYDORUGH3 
GHFUHVFH
2IDWRUGHHVSDOKDPHQWR3 pUHODFLRQDGRDRUDLRGHJLUDomRPpGLRTXDGUiWLFR
s H GHSHQGH GD IRUPD GD PDFURPROpFXOD FRPR SRU H[HPSOR HVIHUDV GLVFRV
2

ILQRVEDVW}HVQRYHORDOHDWyULRHWF
$(TXDomRUHODFLRQDRIDWRUGHHVSDOKDPHQWR3 FRPRUDLRGHJLUDomRGH
XPD PDFURPROpFXOD TXH DSUHVHQWD XPD FRQIRUPDomR VHPHOKDQWH D XP QRYHOR
DOHDWyULRVHQGRDIRUPDFRQVLGHUDGDHVIpULFD

   Q R  
= + 6 VHQ (5.17)
3   
RQGH R p R FRPSULPHQWR GD OX] LQFLGHQWH H QR p R tQGLFH GH UHIUDomR GR PHLR
,QFRUSRUDQGR DV FRUUHo}HV LPSRVWDV SHOR IDWRU GH HVSDOKDPHQWR QD (TXDomR 
FKHJDVHjHTXDomRFRQKHFLGDSRU(TXDomRGH=LPP (TXDomR 

Kc 1 16 2 no2 2 2
= 1 + S sen + 2 A2c + 3 A3c + 
2
(5.18)
R M 3o
2
2

 7pFQLFDSDUD'HWHUPLQDomRGH3HVR0ROHFXODU3RQGHUDO0pGLR
3DUDGHWHUPLQDURSHVRPROHFXODUHRUDLRGHJLUDomRGRQRYHORPDFURPROHFXODU
DUD]mR.F5pFRORFDGDHPJUiILFRYHUVXVRWHUPR>VHQ  NV@$FRQVWDQWHNVp
HVFROKLGD DUELWUDULDPHQWH H XVDGD DSHQDV SDUD VHSDUDU JUDILFDPHQWH DV FXUYDV
LQGLYLGXDLV GR HVSDOKDPHQWR D GLIHUHQWHV FRQFHQWUDo}HV $ )LJXUD  LOXVWUD XP
GLDJUDPD GH HVSDOKDPHQWR FRQKHFLGR FRPR GLDJUDPD GH =LPP 1HVWH GLDJUDPD
GXDVH[WUDSRODo}HVGHYHPVHUIHLWDV
S&RQVLGHUDQGR R kQJXOR FRQVWDQWH H H[WUDSRODQGR j FRQFHQWUDomR ]HUR R
FRHILFLHQWHDQJXODUIRUQHFHRVHJXQGRFRHILFLHQWHYLULDO$
S&RQVLGHUDQGRDFRQFHQWUDomRFRQVWDQWHHH[WUDSRODQGRDRkQJXOR]HURREWpPVH
RFRHILFLHQWHDQJXODU% (TXDomR HDSDUWLUGHVWHRUDLRGHJLUDomR

1 16 2 no2 2
B= S
3o2 (5.19)
M
$V H[WUDSRODo}HV D kQJXOR H FRQFHQWUDomR ]HUR IRUQHFHP R LQYHUVR GR YDORU GR
SHVRPROHFXODUSRQGHUDOPpGLR M w 

)LJXUD'LDJUDPDWRWDOGHHVSDOKDPHQWRGHOX]SHODVROXomRGHPDFURPROpFXODVWDPEpPFRQKHFLGRFRPR
GLDJUDPDGH=LPP

5.1.6 Instrumento utilizado na tcnica de espalhamento de luz


8P HVTXHPD GH XP LQVWUXPHQWR XWLOL]DGR HP DQiOLVHV GH SROtPHURV SRU
HVSDOKDPHQWRGHOX]pDSUHVHQWDGRQD)LJXUD

&DUDFWHUL]DomRGH3ROtPHURV 
)LJXUD6LVWHPDySWLFRGHXPHVSHFWU{PHWURGHHVSDOKDPHQWRGHOX]FRQVWUXtGRSDUDREVHUYDomRD
kQJXORVGHRRH

2LQVWUXPHQWRpFRPSRVWRGDVSDUWHVGHVFULWDVDVHJXLUVHQGRTXHDSUHVHQoDGD
OHQWH PRQRFURPDGRU FROLPDGRU H SRODUL]DGRU LQGLFDGRV QD )LJXUD   QmR p
QHFHVViULDTXDQGRVHXVDODVHUFRPRIRQWHGHOX]
S)RQWHGHOX]2VDQWLJRVHVSHFWU{PHWURVXWLOL]DYDPXPDOkPSDGDGHPHUF~ULR
GHDOWDSUHVVmRFRPRIRQWHGHOX]HPFRQMXQWRFRPXPVLVWHPDGHILOWURVDILP
GHVHREWHUXPIHL[HGHOX]PRQRFURPiWLFD$WXDOPHQWHXWLOL]DVHIHL[HGHODVHU
)HL[HV GH ODVHU VmR LGHDLV SDUD H[SHULPHQWRV HQYROYHQGR HVSDOKDPHQWR GH OX]
SRUTXH D OX] p PRQRFURPiWLFD SHUIHLWDPHQWH FROLPDGD LQWHQVD H SRGH VHU
FRPSOHWDPHQWHSRODUL]DGD
S&pOXODGHPHGLGD$FpOXODGHPHGLGDpFRORFDGDHPXPWHUPRVWDWR$UUDQK}HV
RX FpOXODV PDOOLPSDV FRPSURPHWHP PDLV D PHGLGD GR TXH D IDOWD GH
WHUPRVWDWL]DomR
S'HWHFWRUHVGDOX]HVSDOKDGD2VDSDUHOKRVSRGHPVHUFRQVWUXtGRVGHWDOIRUPD
DSHUPLWLUXPDGHWHFomRDXPkQJXORHVSHFtILFRRXDYiULRVkQJXORV

6LVWHPDVGHGHWHFomRDDSHQDVXPkQJXORSHUPLWHPVRPHQWHGHWHUPLQDURSHVR
PROHFXODU SRQGHUDO PpGLR H IRUQHFHU LQIRUPDo}HV D UHVSHLWR GDV LQWHUDo}HV
SROtPHURVROYHQWHDSDUWLUGDGHWHUPLQDomRGRVHJXQGRFRHILFLHQWHYLULDO&RPRD

 7pFQLFDSDUD'HWHUPLQDomRGH3HVR0ROHFXODU3RQGHUDO0pGLR
GHSHQGrQFLDDQJXODUGDOX]HVSDOKDGDQmRSRGHVHUGHWHUPLQDGDWDLVHTXLSDPHQWRV
QmRSHUPLWHPGHWHUPLQDURUDLRGHJLUDomRGDPDFURPROpFXOD
6LVWHPDV GH GHWHFomR FRP kQJXORV P~OWLSORV SHUPLWHP GHWHUPLQDU R SHVR
PROHFXODURVHJXQGRFRHILFLHQWHGHYLULDOHRUDLRGHJLUDomRRXVHMDRWDPDQKRGD
PDFURPROpFXOD $ )LJXUD  LOXVWUD R HVTXHPD GH XP VLVWHPD GH GHWHFWRUHV
P~OWLSORV

)LJXUD6LVWHPDGHGHWHFWRUHVP~OWLSORVGHXPHVSHFWU{PHWURGHHVSDOKDPHQWRGHOX]DODVHU

$ DPRVWUD FRQWLGD GHQWUR GD FpOXOD GH DQiOLVH HVSDOKD D OX] HP WRGDV DV
GLUHo}HV2HTXLSDPHQWRSRVVXLYiULRVGHWHFWRUHVFRORFDGRVHPWRUQRGDFpOXODGH
DQiOLVHHDGLIHUHQWHVSRVLo}HVDQJXODUHV$UHVSRVWDIRUQHFLGDSRUFDGDGHWHFWRUp
GLUHWDPHQWHSURSRUFLRQDOjLQWHQVLGDGHGDOX]HVSDOKDGD2VVLQDLVVmRWUDQVPLWLGRV
VLPXOWDQHDPHQWH D XP VLVWHPD GH FRPSXWDGRU TXH IRUQHFH GLUHWDPHQWH RV GDGRV
UHIHUHQWHVDRSHVRPROHFXODUVHJXQGRFRHILFLHQWHYLULDOHUDLRGHJLUDomR
$OJXQVHVSHFWU{PHWURVHPSUHJDPGHWHFWRUHVTXHSHUPLWHPPHGLUDLQWHQVLGDGH
GH OX] HVSDOKDGD D SHTXHQR kQJXOR QD IDL[D HQWUH R H R 1HVWHV FDVRV QmR p
QHFHVViULD D H[WUDSRODomR DQJXODU LPSRVWD QR GLDJUDPD GH =LPP 2V YDORUHV GH
M w REWLGRVSRUHVWDWpFQLFDVmRDEVROXWRV(VWDWpFQLFDSRUVHUEDVWDQWHVHQVtYHO
SHUPLWHDXWLOL]DomRGHVROXo}HVEHPGLOXtGDV

5.1.7 Preparao da amostra


2SDUkPHWURQHFHVViULRSDUDDDQiOLVHGDVFDUDFWHUtVWLFDVGHHVSDOKDPHQWRGHXPD
VROXomRpRH[FHVVRGDUD]mRGH5D\OHLJK 5 5VROXomR5VROYHQWH 3RUWDQWRTXDOTXHU
FRQWDPLQDomRSRUSDUWtFXODVGHSRHLUDRXRXWUDVSDUWtFXODVWDQWRQDVROXomRRXQR
VROYHQWH SRGH DFDUUHWDU YDORUHV LQFRUUHWRV GH 5 &RQVHTHQWHPHQWH RV
SDUkPHWURV M w  $ H UDLR GH JLUDomR QmR VHUmR UHSUHVHQWDWLYRV GD VROXomR HP

&DUDFWHUL]DomRGH3ROtPHURV 
DQiOLVH e QHFHVViULR HQWmR HOLPLQDU DR Pi[LPR D TXDQWLGDGH GH SDUWtFXODV HVWUD
QKDV SRHLUDPLFURJpLVRXDJUHJDGRV FRQWLGDVWDQWRQRVROYHQWHTXDQWRQDVROXomR
6ROXo}HVSROLPpULFDVFRQWDPLQDGDVFRPSRHLUDIRUQHFHUmRPDLRUHVYDORUHVGH5
GR TXH VROXo}HV QmR FRQWDPLQDGDV GHYLGR DR WDPDQKR H IRUPD GDV SDUWtFXODV GH
SRHLUD,VWRIRUQHFHUiYDORUHVGH5DFLPDGRVYDORUHVUHDLVVXSHUHVWLPDQGRRSHVR
PROHFXODU SRQGHUDO PpGLR $V UHWDV UHODFLRQDGDV WDQWR j FRQFHQWUDomR TXDQWR DR
kQJXOR WHUmR WDPEpP FRHILFLHQWHV DQJXODUHV PDLRUHV GR TXH RV YDORUHV UHDLV H
SRUWDQWR s 2  H $ DSUHVHQWDUmR YDORUHV PDLRUHV GR TXH DTXHOHV REWLGRV HP
VROXo}HVSROLPpULFDVSXULILFDGDV
$SXULILFDomRGHVROYHQWHVHVROXo}HVH[LJHDWHQomRHVSHFLDOQHVWHVH[SHULPHQWRV
$ SRHLUD H RXWUDV SDUWtFXODV HVWmR VHPSUH SUHVHQWHV HP VROYHQWHV H VROXo}HV QD
DSDUHOKDJHPGHYLGURGHQWURGDFpOXODGHPHGLGDGRHTXLSDPHQWRHQROtTXLGRGR
EDQKR$SUHVHQoDGHSDUWtFXODVHVWUDQKDVQDFpOXODSRGHVHUPLQLPL]DGDDSDUWLUGH
OLPSH]D DSURSULDGD 7DQWR R VROYHQWH TXDQWR D VROXomR GHYHP VHU ILOWUDGRV
XWLOL]DQGRVHILOWURVDSURSULDGRV

5.1.8 Determinao do incremento do ndice de refrao especfico


$UD]mRGH5D\OHLJKGHSHQGHGDSRODUL]DELOLGDGHGDPDFURPROpFXODTXHSRUVXDYH]
p IXQomR GR LQFUHPHQWR GR tQGLFH GH UHIUDomR QF  $ GHWHUPLQDomR GHVWH
SDUkPHWURpIHLWDXWLOL]DQGRXPUHIUDW{PHWURGLIHUHQFLDO8PDFRQILJXUDomRyWLFDGH
XP UHIUDW{PHWUR p H[HPSOLILFDGD QD )LJXUD  8P IHL[H GH OX] PRQRFURPiWLFD
DWUDYHVVD XPD FpOXOD TXH SRVVXL GRLV FRPSDUWLPHQWRV H p PRQWDGD VREUH XP
GLVSRVLWLYR JLUDWyULR (VWHV FRPSDUWLPHQWRV VmR VHSDUDGRV HQWUH VL SRU XPD MDQHOD
SRVLFLRQDGD D XP GHWHUPLQDGR kQJXOR 8P GRV FRPSDUWLPHQWRV GD FpOXOD FRQWpP
DSHQDVVROYHQWHHpGHQRPLQDGRODGRGHUHIHUrQFLD2RXWURODGRGDFpOXODFRQWpPD
VROXomRSROLPpULFD$FpOXODpFRORFDGDGHQWURGHXPEORFRPHWiOLFRWHUPRVWDWL]DGR

)LJXUD5HSUHVHQWDomRJUiILFDGHXPUHIUDW{PHWURGLIHUHQFLDO

 7pFQLFDSDUD'HWHUPLQDomRGH3HVR0ROHFXODU3RQGHUDO0pGLR
$ YDULDomR GR tQGLFH GH UHIUDomR HP IXQomR GD FRQFHQWUDomR p GDGD VHJXQGR D
(TXDomR
n n
= + 1 c + ......
c c (5.20)

&RORFDQGRVH HP JUiILFR RV YDORUHV GH QF YHUVXV F H H[WUDSRODQGRVH j


FRQFHQWUDomR]HURREWpPVHRLQFUHPHQWRGRtQGLFHGHUHIUDomRHVSHFtILFR

5.1.9 Espalhamento de luz dinmico


2 HVSDOKDPHQWR GH OX] GLQkPLFR p GHVFULWR SHOD VLJOD '/6 D TXDO WHP RULJHP QDV
LQLFLDLV GR QRPH HP LQJOrV G\QDPLF OLJKW VFDWWHULQJ 2 '/6 WDPEpP p DOJXPDV
YH]HVGHVLJQDGRHVSDOKDPHQWRGHOX]TXDVHHOiVWLFR TXDVLHODVWLFOLJKWVFDWWHULQJ
4/6 

5.1.9.1 Introduo
$QWLJDPHQWH SHQVDYDVH TXH PROpFXODV HP VROXomR QmR WLQKDP PRYLPHQWR D
PHQRV TXH VH DSOLFDVVH XPD IRUoD H[WHUQD 0DLV WDUGH Mi VH FRQVLGHUDYD R
PRYLPHQWR PROHFXODU FRPR VHQGR HYLGHQWH (VWH PRYLPHQWR PROHFXODU FDXVD
IOXWXDo}HVGHFRQFHQWUDomRHPXPGDGRYROXPHGDVROXomRHPIXQomRGRWHPSR1R
HVSDOKDPHQWR GH OX] GLQkPLFR '/6  D LQWHQVLGDGH GH HVSDOKDPHQWR HP FXUWRV
LQWHUYDORV GH WHPSR  p UHJLVWUDGD FRPR XPD IXQomR GR WHPSR H IOXWXDo}HV QHVVD
LQWHQVLGDGHGHHVSDOKDPHQWRVmRREVHUYDGDVFRPRFRQVHTrQFLDGDVIOXWXDo}HVGH
FRQFHQWUDomRQRYROXPHGHHVSDOKDPHQWR
$ WpFQLFD GH '/6 SHUPLWH D UiSLGD REWHQomR GR FRHILFLHQWH GH GLIXVmR GH
PDFURPROpFXODV HP VROXomR D SDUWLU GD DQiOLVH GD GLVWULEXLomR GH IUHTrQFLD GDV
IOXWXDo}HVQDLQWHQVLGDGHGHOX]HVSDOKDGDHPXPDGDGDGLUHomRLVWRpGHWHFomRGD
LQWHQVLGDGH GH OX] HVSDOKDGD D XP kQJXOR IL[R (VWDV IOXWXDo}HV RULJLQDPVH GDV
YDULDo}HV QR tQGLFH GH UHIUDomR GHQWUR GR YROXPH GH HVSDOKDPHQWR GHYLGR DR
PRYLPHQWR EURZQLDQR GDV SDUWtFXODV 6HQGR DVVLP DV IOXWXDo}HV ORFDLV GHQWUR GR
YROXPHGHHVSDOKDPHQWRHVWmRUHODFLRQDGDVFRPRFRHILFLHQWHGHGLIXVmRDSDUHQWHH
RYHWRUGHRQGDGRHVSDOKDPHQWRVHJXQGRD(TXDomR

= D.q 2 (5.21)

RQGH p D FRQVWDQWH GH FRUUHODomR RX GH UHOD[DomR ' p R FRHILFLHQWH GH GLIXVmR
DSDUHQWHHTpRYHWRUGHRQGDGRHVSDOKDPHQWR
2H[SHULPHQWRGH'/6FRQVLVWHHPREWHUDIOXWXDomRGRVLQDOGHLQWHQVLGDGHGH
OX]HVSDOKDGDFRPRWHPSRUHDOL]DURFiOFXORGDFRUUHODomRGHVVHVYDORUHVHREWHU

&DUDFWHUL]DomRGH3ROtPHURV 
SRUWUDQVIRUPDGDGH)RXULHURHVSHFWURGHIUHTrQFLDVGHIOXWXDomR(VVHHVSHFWUR
pHQWmRDMXVWDGRSRUXPDFXUYDORUHQW]LDQD (TXDomR DSDUWLUGDTXDOREWpP
VH R YDORU GD FRQVWDQWH GH FRUUHODomR *  RX FRQVWDQWH UHOD[DomR XWLOL]DQGRVH R
YDORU GD PHLD DOWXUD j PHLD ODUJXUD GD FXUYD 2 YDORU GR FRHILFLHQWH GH GLIXVmR p
HQWmRFDOFXODGRSRUPHLRGD(TXDomR

G ( ) = A + B exp (2 Dq 2 ) (5.22)

RQGH $ p R YDORU GD OLQKD EDVH H % p R IDWRU SUpH[SRQHQFLDO FRQWHQGR FRQVWDQWHV


ySWLFDVGRHTXLSDPHQWRHGDDPRVWUD
2FRHILFLHQWHGHGLIXVmRDSDUHQWHSRGHFRQWHUFRQWULEXLo}HVWDQWRGRPRYLPHQWR
URWDFLRQDOFRPRGRWUDQVODFLRQDO3DUDVHREWHURFRHILFLHQWHGHGLIXVmRWUDQVODFLRQDO
SXUR 'R pQHFHVViULRH[WUDSRODURFRHILFLHQWHGHGLIXVmRDSDUHQWHDRYHWRUGHRQGD
GH HVSDOKDPHQWR ]HUR 3DUD XPD SDUWtFXOD WLSR EDVWmR HVWD H[WUDSRODomR SRGH VHU
H[SUHVVDSHOD(TXDomR

D = Do (1 + C < S 2 > q 2 ) (5.23)

2 SDUkPHWUR & TXH UHSUHVHQWD D FRQWULEXLomR GH PRYLPHQWRV LQWHUQRV DR


FRHILFLHQWH GH GLIXVmR DSDUHQWH Gi XPD PHGLGD GD IOH[LELOLGDGH QR FDVR GH
HVWUXWXUDVHPFDGHLD3DUDEDVW}HV&WHPXPYDORUWHyULFRGH&RPRDXPHQWR
GD IOH[LELOLGDGH GD FDGHLD & SDVVD SRU XP YDORU Pi[LPR GH  D  H HQWmR
DOFDQoDXPOLPLWHWHyULFRGHSDUDXPDHVWUXWXUDHPQRYHORDOHDWyULR
2UDLRKLGURGLQkPLFRGDVSDUWtFXODV 5+ pREWLGRGH'RXWLOL]DQGRD(TXDomRGH
6WRNHV(LQVWHLQ (TXDomR 

kT
RH = (5.24)
6Do
RQGHNpDFRQVWDQWHGH%ROW]PDQQ7pDWHPSHUDWXUDDEVROXWDH pDYLVFRVLGDGH
GRVROYHQWH
8PDRXWUDIRUPDGHLQWHUSUHWDURVGDGRVGH'/6FRQVLVWHHPDMXVWDUDIXQomRGH
FRUUHODomR* QmRSRUXPDPDVSRUGXDVH[SRQHQFLDLVFRQIRUPHD(TXDomR

G ( ) = A f exp (t / f ) + As exp ((t / se ) ) (5.25)

VHQGR$I$V  
RQGH $I H $V VmR RV PRGRV GH UHOD[DomR UiSLGD H OHQWD UHVSHFWLYDPHQWH VH p XP
GDGRWHPSRGHUHOD[DomRHIHWLYRH  0 < 1 pXPDPHGLGDGDGLVWULEXLomRGRV
WHPSRVGHUHOD[DomR

 7pFQLFDSDUD'HWHUPLQDomRGH3HVR0ROHFXODU3RQGHUDO0pGLR
5.1.9.2 A largura da linha e a funo do tempo de correlao
$LGpLDEiVLFDGR'/6pVLPSOHVHQmRpQRYD2'/6UHVXOWDGRHIHLWR'RSSOHU(VWHp
XPHIHLWREHPFRQKHFLGRGHDFRUGRFRPRTXDODIUHTrQFLDGDIRQWHHPPRYLPHQWR
D PROpFXOD  p GHVORFDGD SDUD YDORUHV PDLV DOWRV RX PDLV EDL[RV VH D IRQWH HVWLYHU
PRYHQGRVH SDUD PDLV SHUWR RX PDLV ORQJH GR GHWHFWRU 2 GHVORFDPHQWR p
SURSRUFLRQDOjUD]mRHQWUHDYHORFLGDGHGDIRQWH HDYHORFLGDGHGHSURSDJDomR
GD RQGD Y 0ROpFXODV QR HVWDGR JDVRVR H HP VROXo}HV PRYHPVH HP WRGDV DV
GLUHo}HVQRHVSDoRHDSUHVHQWDPXPDGLVWULEXLomRGHYHORFLGDGHV(QWmRREVHUYDVH
XPDODUJDPHQWRFRQWtQXRGDOLQKDGHIUHTrQFLDHQmRXPGHVORFDPHQWRGLVFUHWR2
DODUJDPHQWR GD ODUJXUD GD OLQKD p SURSRUFLRQDO DR FRHILFLHQWH GH GLIXVmR
WUDQVODFLRQDO$)LJXUDDPRVWUDRDODUJDPHQWRGDOLQKDHVSHFWUDOHPIXQomRGD
IUHTrQFLD FDXVDGR SHOD GLVWULEXLomR GH YHORFLGDGHV GH PRYLPHQWR GDV PROpFXODV
(IHLWR 'RSSOHU  $ )LJXUD E PRVWUD D IXQomR GH WHPSR GH FRUUHODomR & W 
FRUUHVSRQGHQWHjOLQKDHVSHFWUDODSUHVHQWDGDQD)LJXUDDQRGRPtQLRGHWHPSR

)LJXUD D )RUPD6 GHXPDOLQKDHVSHFWUDOTXHpDODUJDGDSHORHIHLWR'RSSOHUH E IXQomRGRWHPSR


GHFRUUHODomR& W FRUUHVSRQGHQWHQRGRPtQLRGHWHPSR$ODUJXUDGDOLQKDpSURSRUFLRQDODRFRHILFLHQWH
GHGLIXVmRWUDQVODFLRQDO

&DUDFWHUL]DomRGH3ROtPHURV 
5.1.9.3 Funo de tempo de correlao da intensidade de espalhamento
2PRYLPHQWROHQWRGDVPDFURPROpFXODVWRUQDQHFHVViULRWUDEDOKDUHPXPGRPtQLR
GHWHPSRHDSUHQGHUDPDQXVHDURVGDGRV1RHVSDOKDPHQWRGHOX]FRQYHQFLRQDORX
HVWiWLFR HVFROKHVH XP YROXPH GH HVSDOKDPHQWR JUDQGH H XP WHPSR GH UHJLVWUR
ORQJR 6RE WDLV FLUFXQVWkQFLDV WRGDV DV IOXWXDo}HV UHVXOWDQWHV GR PRYLPHQWR GDV
PROpFXODVVmROLGDVFRPRXPDPpGLD1R'/6RYROXPHGHHVSDOKDPHQWRpSHTXHQR
HRWHPSRGHUHJLVWURpFXUWR GDRUGHPGHVRXPHQRU 3RULVVRDLQWHQVLGDGH
GHHVSDOKDPHQWRH[LEHIOXWXDo}HVDFHQWXDGDVFRPRPRVWUDGRHVTXHPDWLFDPHQWHQD
)LJXUD

(A A ) = (A A ) (A A ) = (A A )
N
R
 FDQDO 0 1 i i +1 RFDQDO 0 2 i i+2
1 1

QRFDQDO (A A ) = (A A ) 
0 n i i+n 1 
1

i (0 )i (t ) = A A G (t )
0 n 2



)LJXUD)OXWXDo}HVGDLQWHQVLGDGHGHHVSDOKDPHQWRDWHPSRVFXUWRVHPWRUQRGDPpGLD$!DTXDO
UHSUHVHQWDDLQWHQVLGDGHGHHVSDOKDPHQWRGHOX]HVWiWLFR$LpRQ~PHURGHIyWRQVFKHJDQGRDRGHWHFWRUHP
XPLQWHUYDORGHWHPSRWV1pRQ~PHURGHSURGXWRV$L$LQIRUPDGRVSHORQ~PHURGHIyWRQVQR
LJp]LPRLQWHUYDORGHWHPSRHQR~OWLPRLQWHUYDORGHWHPSRQW

$VIOXWXDo}HVREVHUYDGDVQD)LJXUDQmRUHVXOWDPGDYDULDomRQRQ~PHURGH
PROpFXODVQRYROXPHGHHVSDOKDPHQWRHODVVmRFDXVDGDVSHORDJUXSDPHQWRFDVXDO

 7pFQLFDSDUD'HWHUPLQDomRGH3HVR0ROHFXODU3RQGHUDO0pGLR
GHPROpFXODVRTXDOGiRULJHPDXPDLQWHQVLGDGHGHHVSDOKDPHQWRIRUWHVHJXLGD
SRUXPDGLVVRFLDomRRQGHDLQWHQVLGDGHGHOX]HVSDOKDGDQmRpWmRIRUWH
'HVVH PRGR DV IOXWXDo}HV FRQWrP LQIRUPDo}HV D UHVSHLWR GD PRELOLGDGH GDV
PDFURPROpFXODV 7DLV LQIRUPDo}HV SRGHP VHU REWLGDV GR PRGR GHVFULWR D VHJXLU
7RPHPRV$LFRPRRQ~PHURGHIyWRQVFKHJDQGRQRGHWHFWRUQRLQWHUYDORGHWHPSR
W8WLOL]DQGRXPFRPSXWDGRURQ~PHURGHIyWRQVGHWHFWDGRVHPGRLVLQWHUYDORVGH
WHPSR VXFHVVLYRV VmR PXOWLSOLFDGRV H R SURGXWR p DUPD]HQDGR HP XP SULPHLUR
FDQDO GR FRUUHODWRU (VWH SURFHGLPHQWR p UHSHWLGR FHUFD GH   YH]HV H
DUPD]HQDGRQRFDQDO2VSURGXWRVGHQ~PHURGHIyWRQV$LH$LVmRDUPD]HQDGRV
QRFDQDOHDVVLPVXFHVVLYDPHQWH(YHQWXDOPHQWHQR~OWLPRFDQDOQRVSURGXWRV
GH $L H $LQ VmR FROHWDGRV 2 UHVXOWDGR GHVWD PDQLSXODomR GH GDGRV p PRVWUDGR QD
)LJXUD  SDUD XPD VROXomR RUJkQLFD GH SROtPHUR GH SROLGLVSHUVmR HVWUHLWD $
IXQomR GH GHFDLPHQWR H[SRQHQFLDO p GHQRPLQDGD IXQomR GH WHPSR GH FRUUHODomR
7&)  GD LQWHQVLGDGH GH HVSDOKDPHQWR (VWD GHQRPLQDomR p EDVHDGD QR IDWR GR
LQWHUYDORGHWHPSRHVFROKLGRSDUDRUHJLVWURGHIyWRQVVHUSHTXHQRGHPDLVSDUDTXH
WHQKD RFRUULGR FROLVmR HQWUH D PDLRULD GDV PROpFXODV 3RU LVVR HODV WrP XPD ERD
PHPyULDGDGLUHomRHPDJQLWXGHGHVXDVYHORFLGDGHVGXUDQWHRLQWHUYDORGHWHPSR
LPHGLDWDPHQWHDQWHULRU(QWUHWDQWRDSyVXPORQJRWHPSRGHDWUDVRDVPROpFXODV
WHUmR VRIULGR PXLWDV FROLV}HV H WHUmR SHUGLGR WRGD D PHPyULD GH VXDV YHORFLGDGHV
LQLFLDLV(QWmRDFXUYDPRVWUDGDQD)LJXUDGHVFUHYHRGHFDLPHQWRDSDUWLUGH
XP PRYLPHQWR DOWDPHQWH FRUUHODFLRQDGR SDUD RXWUR FRPSOHWDPHQWH QmR
FRUUHODFLRQDGR e LPSRUWDQWH OHPEUDU TXH DV IOXWXDo}HV RFRUUHP HP WRUQR GH XP
YDORUPpGLR )LJXUD RTXDOpDLQWHQVLGDGHGHHVSDOKDPHQWRTXHpUHJLVWUDGD
SHORHVSDOKDPHQWRGHOX]HVWiWLFR

5.1.10 Exemplos de aplicaes


5.1.10.1 Caracterizao de copolmeros
&RPR PHQFLRQDGR QR WH[WR R HVSDOKDPHQWR GH OX] HVWiWLFR 6/6  SHUPLWH
GHWHUPLQDU R SHVR PROHFXODU SRQGHUDO PpGLR M w  R UDLR GH JLUDomR 6  H R
VHJXQGRFRHILFLHQWHYLULDO $ 4XDQGRUHVXOWDGRVGHKRPRSROtPHURVVmRDQDOLVDGRV
DVVXPHVH VHPSUH TXH WRGDV DV PROpFXODV SRVVXHP R PHVPR tQGLFH GH UHIUDomR H
TXH HODV GLIHUHP VRPHQWH QR SHVR PROHFXODU 2 FDVR GH FRSROtPHURV TXH VmR
KHWHURJrQHRVQDFRPSRVLomRTXtPLFDFRQVWLWXLXPDH[FHomRjUHJUD

&DUDFWHUL]DomRGH3ROtPHURV 
)LJXUD)XQomRGRWHPSRGHFRUUHODomRGDLQWHQVLGDGHGHHVSDOKDPHQWR* W  L  L W !GHXPD
VROXomRRUJkQLFDGHSROtPHURSROLGLVSHUVRFRPRXPDIXQomRGRWHPSRGHDWUDVR

4XDQGR RV FRSROtPHURV VmR SUHSDUDGRV p SUDWLFDPHQWH LPSRVVtYHO REWHU


PROpFXODV GH FRPSRVLomR XQLIRUPH &RQVHTHQWHPHQWH FRPR R tQGLFH GH UHIUDomR
GHSHQGH GD FRPSRVLomR DV UHJUDV FOiVVLFDV VXVWHQWiYHLV HP XP VLVWHPD
SROLGLVSHUVR QmR VmR DSOLFiYHLV $OpP GLVVR HP FHUWRV FDVRV RV YiULRV WLSRV GH
VHTrQFLD RFXSDP SRVLo}HV GLVWLQWDV HP UHODomR DR FHQWUR GH JUDYLGDGH GD
PROpFXOD'HVWHPRGRDGLVWULEXLomRDQJXODUGHOX]HVSDOKDGDpFRQVLGHUDYHOPHQWH
GLIHUHQWHGDTXHODHQFRQWUDGDQRFDVRGHKRPRSROtPHURV
$VVLP R YDORU GH SHVR PROHFXODU FDOFXODGR D SDUWLU GR HVSDOKDPHQWR GH OX]
HVWiWLFR 6/6 pQDYHUGDGHXPSHVRPROHFXODUSRQGHUDOPpGLRDSDUHQWH M app R
TXDO YDULD FRP R tQGLFH GH UHIUDomR GR VROYHQWH XWLOL]DGR QR SUHSDUR GD VROXomR
SDUDXPDPHVPDDPRVWUDGHFRSROtPHUR
(VWXGRV HQYROYHQGR FDUDFWHUL]DomR GH SHVR PROHFXODU GH FRSROtPHURV SRU
HVSDOKDPHQWR GH OX] HVWiWLFR FLWDP R XVR GH VROYHQWH LVRUUHIUDWLYRV 6ROYHQWH
LVRUUHIUDWLYRpDTXHOHTXHHPXPVLVWHPDGHGRLVFRPSRQHQWHV$H%SRVVXLtQGLFH
UHIUDomRLJXDOjTXHOHGHXPGRVFRPSRQHQWHV'HVWHPRGRDWpFQLFDVypFDSD]GH
GHWHFWDU R FRPSRQHQWH FRP tQGLFH GH UHIUDomR GLIHUHQWH GDTXHOH GR VROYHQWH
XWLOL]DGR $VVLP XWLOL]DQGR XP VROYHQWH LVRUUHIUDWLYR SDUD R FRPSRQHQWH $ p
SRVVtYHOGHWHUPLQDURSHVRPROHFXODUGDVHTrQFLD%(PRXWUDDQiOLVHXWLOL]DQGR
VH XP VROYHQWH LVRUUHIUDWLYR SDUD R FRPSRQHQWH % p SRVVtYHO GHWHUPLQDU R SHVR
PROHFXODUGDVHTrQFLD$1HVWHFDVRRVYDORUHVGHSHVRPROHFXODUVmRFDOFXODGRV
FRPR GHVFULWR DQWHULRUPHQWH UHDOL]DQGR D DQiOLVH FRP VROXo}HV GH FRQFHQWUDo}HV

 7pFQLFDSDUD'HWHUPLQDomRGH3HVR0ROHFXODU3RQGHUDO0pGLR
YDULDGDVGHWHFWDQGRDLQWHQVLGDGHGHHVSDOKDPHQWRDkQJXORVWDPEpPYDULDGRVH
FRQVWUXLQGRRJUiILFRGH=LPP

5.1.10.2 Caracterizao de agregao molecular


$V DQiOLVHV SDUD GHWHUPLQDomR GH SHVR PROHFXODU VmR UHDOL]DGDV HP JHUDO HP
FRQFHQWUDo}HV GLOXtGDV D ILP GH DVVHJXUDU R HVWDGR QmRDVVRFLDGR GDV PROpFXODV
3DUDFRQFHQWUDo}HVPDLVHOHYDGDVQDVTXDLVDVPROpFXODVHQFRQWUDPVHDVVRFLDGDV
D WpFQLFD GH HVSDOKDPHQWR GH OX] QmR p FDSD] GH GHWHUPLQDU R SHVR PROHFXODU GH
XPD PROpFXOD LVRODGD PDV VLP GR DJUHJDGR FRPR XP WRGR (VWH IDWR p ~WLO QD
GHWHUPLQDomR GD IRUPDomR GH DJUHJDGRV PROHFXODUHV H SHUPLWH DLQGD FDOFXODU R
Q~PHURGHPROpFXODVSUHVHQWHVQRDJUHJDGRHPFDGDFRQFHQWUDomR'HXPPRGR
EDVWDQWHVLPSOHVDIRUPDomRGRDJUHJDGRHPIXQomRGDFRQFHQWUDomRWHPSHUDWXUD
RX TXDOLGDGH GR VROYHQWH SRGH VHU GHWHFWDGD TXDQGR R YDORU GR SHVR PROHFXODU
FDOFXODGR DXPHQWD $ SDUWLU GR YDORU GR SHVR PROHFXODU FDOFXODGR SDUD VROXo}HV
GLOXtGDV H GR SHVR PROHFXODU FDOFXODGR SDUD R DJUHJDGR p SRVVtYHO FDOFXODU R
Q~PHURPpGLRGHPROpFXODVTXHFRQVWLWXHPRDJUHJDGR
2XWUR PRGR GH REVHUYDU D IRUPDomR GH DJUHJDGRV PROHFXODUHV HP XPD DPSOD
IDL[DGHFRQFHQWUDomRGDVVROXo}HVpDWUDYpVGRSHUILOGRJUiILFRGH=LPPREWLGR
(PJHUDORJUiILFRGH=LPPpFRQVWLWXtGRSRUYiULDVUHWDVDVTXDLVVmRH[WUDSRODGDV
SDUDFRQFHQWUDomRHkQJXOR]HUR YHU)LJXUD 1RFDVRGHVLVWHPDVHPTXHKiD
IRUPDomR GH DJUHJDGRV QD IDL[D GH FRQFHQWUDomR DQDOLVDGD R JUiILFR GH =LPP
DSUHVHQWDVHFRPRFXUYDV )LJXUD eLPSRUWDQWHOHPEUDUHQWUHWDQWRTXHHP
FRQGLo}HV DGYHUVDV GH DQiOLVH SRHLUD OX] H[WHUQD HP H[FHVVR HWF  R JUiILFR GH
=LPPWDPEpPVHDSUHVHQWDQDIRUPDGHFXUYDVPHVPRSDUDVROXo}HVGHPROpFXODV
QmRDJUHJDGDV

)LJXUD'LDJUDPDGH=LPPSDUDXPVLVWHPDKLSRWpWLFRQRTXDOHVWiRFRUUHQGRDVVRFLDomRPROHFXODU

&DUDFWHUL]DomRGH3ROtPHURV 
$IRUPDomRGHDJUHJDGRVPROHFXODUHVWDPEpPSRGHVHUGHWHFWDGDSRUHVSDOKD
PHQWRGHOX]GLQkPLFR3DUDWDQWRGHYHPVHUSUHSDUDGDVYiULDVVROXo}HVGHFRQFHQ
WUDo}HVYDULDGDV3DUDFDGDFRQFHQWUDomRREWpPVHXPFRHILFLHQWHGHGLIXVmR([WUD
SRODQGRVHRVYDORUHVGHFRHILFLHQWHGHGLIXVmRSDUDFRQFHQWUDomR]HURREWpPVHR
YDORUGH'R'HSRVVHGRYDORUGH'RHXWLOL]DQGRD(TXDomRGH6WRNHV(LQVWHLQ  
pSRVVtYHOGHWHUPLQDURYDORUGRUDLRKLGURGLQkPLFR5+2UDLRKLGURGLQkPLFRGHXP
SROtPHUR HP XP PHVPR VROYHQWH QD PHVPD WHPSHUDWXUD YDULD HP IXQomR GR
HVWDGRGHDJUHJDomRGDVPROpFXODV

5.1.10.3 Sistemas combinados


2VHTXLSDPHQWRVGHHVSDOKDPHQWRGHOX]SRGHPVHUDFRSODGRVFRPRXWURVVLVWHPDV
GHDQiOLVH2HVSDOKDPHQWRGHOX]pSRUH[HPSORPXLWRXWLOL]DGRFRPRGHWHFWRUHP
FURPDWRJUDILDGHH[FOXVmRSRUWDPDQKR YHUFDStWXORLWHP 


5.2 Ultracentrifugao

5.2.1 Introduo
4XDQGR SDUWtFXODV PDFURVFySLFDV HP XP OtTXLGR GHSRVLWDPVH VRE D DomR GD
JUDYLGDGHpSRVVtYHOGHWHUPLQDUVHXWDPDQKRHSHVR0DFURPROpFXODVHPVROXomR
QRUPDOPHQWHDSUHVHQWDPWDPDQKRVPXLWRPHQRUHVHOHYDULDPDQRVSDUDVXSHUDUR
PRYLPHQWREURZQLDQRHIRUPDUXPVHGLPHQWR(VWHSUREOHPDSRGHVHUFRQWRUQDGR
VXEPHWHQGR DV PROpFXODV D XPD IRUoD H[WHUQD IRUWH R VXILFLHQWH SDUD DOWHUDU VXD
GLVWULEXLomR HVSDFLDO GH PRGR VLJQLILFDWLYR HP XP SHUtRGR GH WHPSR FXUWR (VWH
REMHWLYRIRLSULPHLUDPHQWHDOFDQoDGRSRU6YHGEHUJHPVROXo}HVSROLPpULFDV
IRUDP VXEPHWLGDV D FDPSRV GH IRUoD LQWHQVRV JHUDGRV FRP DOWDV YHORFLGDGHV GH
URWDomR
$ DQiOLVH GH VHGLPHQWDomR IRUQHFH YDORUHV DEVROXWRV GH SHVR PROHFXODU FRP
PXLWRERDSUHFLVmRHpDSOLFiYHODXPDH[WHQVDIDL[DGHSHVRVPROHFXODUHV GHD
 DSUR[LPDGDPHQWH  $OpP GLVVR IRUQHFH LQIRUPDo}HV SUHFLVDV VREUH
SURSULHGDGHVKLGURGLQkPLFDVGHPDFURPROpFXODVEHPFRPRGDGRVWHUPRGLQkPLFRV
YDOLRVRV$WpFQLFDUHTXHUXPDTXDQWLGDGHPXLWRSHTXHQDGHPDWHULDOHPJHUDO
JGHDPRVWUDVmRVXILFLHQWHVSDUDPHGLUSHVRPROHFXODUHSROLGLVSHUVmR
(QWUHWDQWR DV PHGLGDV GH VHGLPHQWDomR VmR HP JHUDO WHGLRVDV H FRQVRPHP
PXLWR WHPSR &RP R DGYHQWR SRVWHULRU GH RXWUDV WpFQLFDV GH FDUDFWHUL]DomR GH
SROtPHURVWDLVFRPRHVSDOKDPHQWRGHOX]FURPDWRJUDILDGHH[FOXVmRSRUWDPDQKR
6(&  PHGLGDV UHROyJLFDV H HVSHFWURVFRSLD D DQiOLVH GH VHGLPHQWDomR HVWi VHQGR
IUHTHQWHPHQWH PHQRV XWLOL]DGD (VWH IHQ{PHQR p FRPSUHHQVtYHO XPD YH] TXH
RXWURV PpWRGRV IRUQHFHP DV LQIRUPDo}HV GHVHMDGDV FRP PDLRU IDFLOLGDGH

 7pFQLFDSDUD'HWHUPLQDomRGH3HVR0ROHFXODU3RQGHUDO0pGLR
(QWUHWDQWRRPpWRGRGHVHGLPHQWDomRVREUHYLYHFRPH[FHomRGRHVSDOKDPHQWRGH
OX]HVWHpR~QLFRPpWRGRTXHIRUQHFHSHVRPROHFXODUSRQGHUDOPpGLRDEVROXWRXVD
TXDQWLGDGHVPXLWRSHTXHQDVGHPDWHULDOHpH[WUHPDPHQWHIOH[tYHO

5.2.2 O equipamento
$ XOWUDFHQWUtIXJD DQDOtWLFD p XP HTXLSDPHQWR TXH SHUPLWH D REVHUYDomR GD
GLVWULEXLomRGHFRQFHQWUDomRHPXPDVROXomRTXDQGRHVWDHVWiVXMHLWDDXPFDPSR
FHQWUtIXJR 2 HTXLSDPHQWR p FRQVWLWXtGR EDVLFDPHQWH GH XPD FpOXOD QD TXDO D
DPRVWUD p FRORFDGD  XP URWRU XP VLVWHPD GH FRQWUROH GH YHORFLGDGH GH
URWDomRWHPSHUDWXUDHXPVLVWHPDySWLFRGHGHWHFomRGDFRQFHQWUDomR$VROXomRp
FRORFDGD GHQWUR GD FpOXOD TXH HVWi HQFDL[DGD QR URWRU H HQWmR VXEPHWLGD D
YHORFLGDGHVGHRXUSPSRUXPPRWRUHOpWULFR$)LJXUDPRVWUDR
HVTXHPDGHXPDXOWUDFHQWUtIXJD

)LJXUD5HSUHVHQWDomRHVTXHPiWLFDGHXPDXOWUDFHQWUtIXJD

S$FpOXOD([LVWHPGLYHUVRVWLSRVGHFpOXODVGLVSRQtYHLVHVXDHVFROKDGHSHQGHGH
TXDVH WRGDV DV FRQGLo}HV GR H[SHULPHQWR WLSR GH H[SHULPHQWR PpWRGR GH
GHWHUPLQDomR YHORFLGDGH GH VHGLPHQWDomR RX HTXLOtEULR GH VHGLPHQWDomR 
WHPSHUDWXUD VROYHQWH WLSR GH VLVWHPD ySWLFR FRQFHQWUDomR GD DPRVWUD
DQDOLVDGD 'H XP PRGR JHUDO D FpOXOD p FRQVWLWXtGD GH XPD SHoD FHQWUDO TXH
VHSDUD GXDV MDQHODV $ FDGD XPD GDV MDQHODV p FRQHFWDGR XP VXSRUWH DQpLV GH
YHGDomRHURVFDV$VMDQHODVRSWLFDPHQWHDFKDWDGDVSRGHPVHUFRQIHFFLRQDGDV
HP TXDUW]R RX VDILUD $ SHoD FHQWUDO FRQWpP XP RULItFLR QR TXDO D DPRVWUD p
LQVHULGD DV SDUHGHV GR FDQDO GHOLPLWDP XP VHWRU GH XP FLOLQGUR GHILQLGR SHOR

&DUDFWHUL]DomRGH3ROtPHURV 
HL[RGHURWDomRGHPRGRTXHDVPROpFXODVGRVROXWRLUmRVHPSUHVHGLPHQWDUHP
XPDGLUHomRUDGLDO
S2 URWRU  9iULRV WLSRV GH URWRUHV HVWmR GLVSRQtYHLV GLIHULQGR QD PDVVD H QR
Q~PHUR GH FpOXODV TXH LUmR DFRPRGDU 5RWRUHV GH TXDWUR D VHLV OXJDUHVWRUQDP
SRVVtYHO D REVHUYDomR VLPXOWkQHD GH PXLWDV FpOXODV HPERUD WDLV URWRUHV VHMDP
UHVWULWRVDYHORFLGDGHVPHQRUHVGRTXHDTXHODVDOFDQoDGDVFRPURWRUHVOHYHVGH
GRLV OXJDUHV 2V URWRUHV PDLV SHVDGRV GH GRLV RX PDLV OXJDUHV LUmR DFRPRGDU
FpOXODV FRP SHoDV FHQWUDLV GH FDPLQKR ySWLFR GH PP 'HYLGR j PDVVD H DR
EDL[RFHQWURGHJUDYLGDGHHVVHVURWRUHVVmRUHODWLYDPHQWHHVWiYHLVDYHORFLGDGHV
EDL[DVPDVQmRSRGHPVHUVXEPHWLGRVDYHORFLGDGHVHOHYDGDV
S2 VLVWHPD GH FRQWUROH  2 URWRU HVWi ORFDOL]DGR GHQWUR GH XPD FkPDUD GH YiFXR
PyYHO (P HTXLSDPHQWRV PDLV DQWLJRV D YHORFLGDGH GR URWRU p PDQWLGD
FRQVWDQWH SRU FRPSDUDomR FRP D URWDomR GH XP PRWRU VLQFURQL]DGR (P
HTXLSDPHQWRVPDLVPRGHUQRVHODpFRQWURODGDSRUXPVLVWHPDIRWRHOpWULFRFXMD
VDtGDpXVDGDSDUDUHJXODUDFRUUHQWHDWUDYpVGRPRWRU$WHPSHUDWXUDGRURWRUp
PRQLWRUDGD SRU XP WHUPLVWRU ORFDOL]DGR HP VXD EDVH H p UHJXODGD SRU
VHUSHQWLQDV GH UHIULJHUDomR GLVSRVWDV HP WRUQR GD FkPDUD GH YiFXR H SRU XP
VLVWHPDGHDTXHFLPHQWRSRVLFLRQDGRQDEDVHGHVVDFkPDUD'HXPPRGRJHUDOp
SRVVtYHOFRQWURODUDWHPSHUDWXUDQDIDL[DGHD&HTXLSDPHQWRVHVSHFLDLV
SRGHPDWLQJLUDWHPSHUDWXUDGH&
S2 VLVWHPD ySWLFR  )RQWHV GH OX] VmR SRVLFLRQDGDV GH PRGR TXH R IHL[H SDVVH
DWUDYpVGHXPDOHQWHFROLPDGRUDORFDOL]DGDQDEDVHGDFkPDUDGHYiFXRHDWLQMD
RURWRURTXDOLQWHUURPSHRIHL[HGHOX]H[FHWRTXDQGRDFpOXODHVWiQRFDPLQKR
ySWLFR2IHL[HTXHDWUDYHVVDDFpOXODSDVVDDWUDYpVGHXPDOHQWHFRQGHQVDGRUD
ORFDOL]DGDQRWRSRGDFkPDUDpGHVYLDGRHPSRUXPHVSHOKRSDVVDDWUDYpV
GR UHVWDQWH GR VLVWHPD ySWLFR GHQWUR GH XP WXER KRUL]RQWDO H FKHJD j SODFD
IRWRJUiILFDRXDRIRWRPXOWLSOLFDGRUGHDEVRUomR

(P UHVXPR GHVHMDVH PHGLU D FRQFHQWUDomR GR VROXWR RX VHX JUDGLHQWH GH
FRQFHQWUDomR FRPRXPDIXQomRGDSRVLomRUDGLDO2VVLVWHPDVySWLFRVPDLVFRPXQV
DFRPSDQKDP D FRQFHQWUDomR SHOD PHGLGD GH LQFUHPHQWR GH tQGLFH GH UHIUDomR RX
DEVRUomRGHOX]
$ GLVWULEXLomR GH FRQFHQWUDomR GHQWUR GD FpOXOD GH VHGLPHQWDomR p REWLGD GH
PRGR PDLV FRQYHQLHQWH D SDUWLU GH YDUUHGXUDV XVDQGR OX] XOWUDYLROHWD 89  GH
FRPSULPHQWR GH RQGD DSURSULDGR (VWH PRGR p PXLWR ~WLO SDUD PDWHULDLV
ELRTXtPLFRVGLVVROYLGRVHPWDPS}HVDTXRVRVPDVUDUDPHQWHSRGHVHUXVDGRSDUD
SROtPHURVHPVROYHQWHVRUJkQLFRV3RUXPODGRPXLWRVSROtPHURVQmRDSUHVHQWDP
TXDOTXHUDEVRUomRQRVFRPSULPHQWRVGHRQGDGLVSRQtYHLVSRURXWURODGRVROYHQWH
FRPIXQomRFDUERQLODKDORJHQDGRVDURPiWLFRVHRXWURVSRGHPDEVRUYHUQDUHJLmR

 7pFQLFDSDUD'HWHUPLQDomRGH3HVR0ROHFXODU3RQGHUDO0pGLR
GR893RUH[HPSORDDEVRUomRPi[LPDGHFRPSRVWRVFRQWHQGRFDUERQLODHVWiHP
WRUQR GH  QP -i QR HVWDGR OtTXLGR HP XPD FDPDGD GH PP HOHV VmR
YLUWXDOPHQWHRSDFRVSDUDDPDLRULDGRVFRPSULPHQWRVGHRQGDQDUHJLmRGR896RE
WDLV FLUFXQVWkQFLDV D PHGLGD GR SHUILO GH FRQFHQWUDomR PDLV LQGLFDGD WHP TXH VHU
EDVHDGDQDYDULDomRGRtQGLFHGHUHIUDomR

5.2.3 Procedimento de anlise


$VROXomRGLOXtGDGRSROtPHURpFRORFDGDHPXPDFpOXODFRPXPDSHoDFHQWUDOQD
IRUPD GH FRQH WUXQFDGR FXMR YpUWLFH HVWi ORFDOL]DGR QR FHQWUR GH URWDomR 7DO
IRUPDWR DVVHJXUD TXH GLVW~UELRV FRQYHFWLYRV VHMDP PLQLPL]DGRV GXUDQWH R
WUDQVSRUWH GDV PROpFXODV SDUD R IXQGR GD FpOXOD $V FpOXODV VmR DSRLDGDV HP XP
URWRU FRQVWLWXtGR SRU OLJD GH WLWkQLR RX DOXPtQLR  R TXDO p SUHVR D XP PRWRU SRU
XP ILR GH DoR ILQR 2 URWRU p JLUDGR HP XPD FkPDUD GH YiFXR SDUD PLQLPL]DU R
DTXHFLPHQWR IULFFLRQDO GXUDQWH D DSOLFDomR GH DOWDV YHORFLGDGHV GH URWDomR GD
RUGHPGHUSP'XUDQWHDURWDomRXPIHL[HGHOX]FROLPDGR SURYHQLHQWHGH
XPD OkPSDGD GH PHUF~ULR GH DOWD SUHVVmR  SDVVD DWUDYpV GD FpOXOD H RIHL[HHPHU
JHQWH YLDMD DWUDYHVVD R VLVWHPD ySWLFR SDUD VHU UHJLVWUDGR IRWRJUDILFDPHQWH 7UrV
WLSRVGHVLVWHPDVySWLFRVHVWmRGLVSRQtYHLV6FKOLHUHQLQWHUIHUrQFLDDEVRUomR89
2 VROYHQWH GHYH VHU HVFROKLGR FRP FXLGDGR GH PRGR D DSUHVHQWDU YDORUHV GH
GHQVLGDGHHGHtQGLFHGHUHIUDomRVXILFLHQWHPHQWHGLIHUHQWHVGDTXHOHVGRSROtPHUR
L,VWR p R PRYLPHQWR GD FDGHLD SROLPpULFD QR PHLR H D GHWHFomR ySWLFD GHVVH
PRYLPHQWRGHYHPVHUDVVHJXUDGRVSHODHVFROKDDGHTXDGDGRVROYHQWH
$ PDLRULD GRV LQVWUXPHQWRV FRPHUFLDLV p H[WUHPDPHQWH YHUViWLO FRP XPD
JUDQGH YDULHGDGH GH HVFROKD SDUD YHORFLGDGH GR URWRU H VLVWHPDV GH FRQWUROH GH
WHPSHUDWXUD
(VWD WpFQLFD SHUPLWH DQDOLVDU DPRVWUDV GH SROtPHUR FRP SHVRV PROHFXODUHV QD
IDL[DGHD(VWDIDL[DpPXLWRPDLVDPSODGRTXHHPTXDOTXHURXWUDWpFQLFD
H[LVWHQWH
'RLV PpWRGRV JHUDLV VmR XVDGRV SDUD PHGLU SHVR PROHFXODU SRU PHLR GH
XOWUDFHQWULIXJDomR EDVHDGRV HP   YHORFLGDGH GH VHGLPHQWDomR H   HTXLOtEULR GH
VHGLPHQWDomR2VUHVXOWDGRVIRUQHFLGRVSHORPpWRGRGHYHORFLGDGHGHVHGLPHQWDomR
HP SULQFtSLR VmR PHQRV ULJRURVRV TXH DTXHOHV REWLGRV SRU HTXLOtEULR GH
VHGLPHQWDomR(QWUHWDQWRQDSUiWLFDSRUVHUGHPDLVIiFLOXWLOL]DomRRPpWRGRGH
YHORFLGDGHGHVHGLPHQWDomRWHPVLGRPDLVHPSUHJDGR

5.2.4 Velocidade de sedimentao


2 PpWRGR GH YHORFLGDGH GH VHGLPHQWDomR WHP VLGR XVDGR SDUD GRLV SURSyVLWRV
SULQFLSDLVFRPRXPFULWpULRGHSXUH]DGHPDWHULDLVELRTXtPLFRVHSDUDDPHGLGDGH

&DUDFWHUL]DomRGH3ROtPHURV 
FRHILFLHQWHVGHVHGLPHQWDomR K sed (VWHFRHILFLHQWHVHUYHSDUDDFDUDFWHUL]DomRGH
PDWHULDLVHSDUDFiOFXORVGHSHVRPROHFXODUHSURSULHGDGHVKLGURGLQkPLFDV
$ FHQWUtIXJD p RSHUDGD D DOWDV YHORFLGDGHV SDUD WUDQVSRUWDU PROpFXODV GH
SROtPHURDWUDYpVGRVROYHQWHSDUDRIXQGRGDFpOXODVHDGHQVLGDGHGRVROYHQWHIRU
PHQRUTXHDGRSROtPHURRXSDUDRWRSR IORWDomR VHDGHQVLGDGHGRVROYHQWHIRU
PDLRU TXH D GR SROtPHUR $ WD[D GH PRYLPHQWR SRGH VHU PRQLWRUDGD SRU PHLR GD
YDULDomRQRtQGLFHGHUHIUDomR n QDUHJLmROLPLWH$UHJLmROLPLWHRQGHRIHL[HGH
OX]LUiLQFLGLUpLGHQWLILFDGDSRUXPDYDULDomREHPGHILQLGDQRtQGLFHGHUHIUDomRH
VHX PRYLPHQWR p DFRPSDQKDGR FRPR XPD IXQomR GR WHPSR XVDQGR XP GRV
PpWRGRV ySWLFRV GLVSRQtYHLV  PHGLGD TXH DV PROpFXODV VHGLPHQWDPVH XPD
FDPDGDGHVROYHQWHSXURpIRUPDGDFXMRtQGLFHGHUHIUDomRpGLIHUHQWHGDTXHOHGD
VROXomR
$PROpFXODGHSROtPHURPRYLPHQWDQGRVHDWUDYpVGDVROXomRLUiH[SHULPHQWDU
XPDIRUoDFHQWUtIXJD F  (TXDomR PDVDVPROpFXODVGHVORFDPXPDPDVVDGH
VROXomR mo  (TXDomR   H LUmR HVWDU VXMHLWDV D XP HIHLWR GH IOXWXDomR H D XPD
IRUoDRSRVWD F  (TXDomR 
F = 2 rm (5.26)

mo = m 2 (5.27)

F = 2 rm 2 (5.28)

RQGH pDYHORFLGDGHDQJXODUGHURWDomR r pDGLVWkQFLDHQWUHDUHJLmROLPLWHHR


FHQWURGHURWDomR 2 pRYROXPHHVSHFtILFRSDUFLDOGRSROtPHUR pDGHQVLGDGH
GDVROXomRH m pDPDVVDGDPROpFXOD m = M / N A  M  SHVRPROHFXODUH N A  
Q~PHURGH$YRJDGUR 
$IRUoDOtTXLGDHQWUH F H F VHUiGDGDHQWmRSHOD(TXDomR
F = m 2 r m 2 r 2 = m (1 2 )r 2 = ( M / N A )(1 2 )r 2 (5.29)
(VWD IRUoD VHUi EDODQFHDGD SHOD UHVLVWrQFLD IULFFLRQDO GR PHLR SDUD XPD  GDGD
YHORFLGDGH dr / dt H
F = 6RS (dr / dt ) (5.30)

RQGH RS  p R UDLR GD SDUWtFXOD HVIpULFD GR SROtPHUR H  p D YLVFRVLGDGH GR PHLR
(VWDVGXDVIRUoDVHVWmRHPHTXLOtEULRTXDQGRXPDYHORFLGDGHGHSDUWtFXODXQLIRUPH
pDOFDQoDGDH
( M / N A )(1 2 )r 2 = 6RS (dr / dt ) (5.31)

 7pFQLFDSDUD'HWHUPLQDomRGH3HVR0ROHFXODU3RQGHUDO0pGLR
$ YHORFLGDGH QR HVWDGR HVWDFLRQiULR HP XPD XQLGDGH GH FDPSR JUDYLWDFLRQDO
SRGHHQWmRVHUGHILQLGDFRPRDFRQVWDQWHGHVHGLPHQWDomR K sed 
K sed = (1 / 2 r )(dr / dt ) (5.32)

$SDUWLUGD(TXDomRWHPVHTXH
(1 / 2 r )(dr / dt ) = ( M / N A )(1 2 ) / 6RS HQWmR
K sed = ( M / N A )(1 2 ) / 6RS = ( M / N A )(1 2 ) / f (5.33)

RQGH f  p R FRHILFLHQWH GH IULFomR GD PROpFXOD H HVWi UHODFLRQDGR j FRQVWDQWH GH
GLIXVmR D SHOD(TXDomR
D = kT / f (5.34)

RQGH k pDFRQVWDQWHGH%ROW]PDQQH T DWHPSHUDWXUDDEVROXWD$(TXDomRp


XVDGD WDQWR SDUD FDOFXODU R FRHILFLHQWH GH IULFomR TXDQGR M  p FRQKHFLGR SRU
H[HPSORSRUGDGRVGHHVSDOKDPHQWRGHOX] FRPRSDUDFDOFXODUSHVRPROHFXODUVH
f pFRQKHFLGRDSDUWLUGHPHGLGDVGHFRHILFLHQWHGHGLIXVmR D 
5HDUUDQMDQGRDVHTXDo}HVDQWHULRUHVREWpPVHDHTXDomRGH6YHGEHUJ (TXDomR
 
M SD = [ RT /(1 2 )]( K sed / D) (5.35)

$ SDUWLU GD (TXDomR  H FRQKHFHQGRVH Ksed H D  R SHVR PROHFXODU M SD 


SRGHVHUFDOFXODGR2YDORUGH M SD pSUy[LPRDRGH M w PDVHPJHUDOpPHQRUH
GHSHQGHGRPpWRGRXVDGRSDUDPHGLU D 
2 WHUPR (1 2 )  p GHQRPLQDGR IDWRU GH IOXWXDomR H GHWHUPLQD D GLUHomR GH
WUDQVSRUWH PROHFXODU QD FpOXOD 6H HVWH IDWRU p SRVLWLYR DV FDGHLDV GH SROtPHUR
VHGLPHQWDPVHGRFHQWURGHURWDomRSDUDRIXQGRGDFpOXODVHQHJDWLYRDVFDGHLDV
PRYHPVHQRVHQWLGRRSRVWRHIOXWXDPQRWRSR
1D YHUGDGH GDGRV PHGLGRV FXLGDGRVDPHQWH SRGHP OHYDU D YDORUHV GH SHVR
PROHFXODUTXHVXSHUDPHPH[DWLGmRRVGDGRVREWLGRVSRURXWURVPpWRGRV(DLQGD
RV FRHILFLHQWHV GH IULFomR SRGHP VHUYLU FRPR EDVH SDUD XPD DQiOLVH GHWDOKDGD GH
FRQVWDQWHVKLGURGLQkPLFDVEiVLFDV
$GHWHUPLQDomRGH M pDEVROXWDTXDQGR K sed H D VmRFRQKHFLGRV
$ PHGLGD SULPiULD IHLWD SRU HVWH PpWRGR p GH GLVWULEXLomR GH FRHILFLHQWHV GH
VHGLPHQWDomR g ( K sed )  (VWD GLVWULEXLomR XPD YH] GHWHUPLQDGD SRGH VHU
WUDQVIRUPDGD HP GLVWULEXLomR GH SHVRV PROHFXODUHV f (M )  XVDQGR XPD UHODomR
DGHTXDGD



&DUDFWHUL]DomRGH3ROtPHURV 
Como obter K sed a partir dos experimentos ?

S&RHILFLHQWHV GH VHGLPHQWDomR K sed   8P VROXWR PDFURPROHFXODU KRPRJrQHR


SRGH VHU GHVFULWR HP XP GDGR VROYHQWH SRU XP FRHILFLHQWH GH VHGLPHQWDomR R
TXDOpGHILQLGRFRPRDWD[DGHPRYLPHQWRGRVROXWRHPXPDGLUHomRUDGLDOSRU
XQLGDGHGHFDPSR&RPRPRVWUDGRQD)LJXUDRPRYLPHQWRGRVROXWRFULD
XPDLQWHUIDFHPDLVRXPHQRVGLIXVDHQWUHDUHJLmRFHQWUtIXJDRQGHRJUDGLHQWH
GHFRQFHQWUDomRpHVVHQFLDOPHQWH]HUR RSDWDPDU HDUHJLmRFHQWUtSHWDRQGHD
FRQFHQWUDomR GH VROXWR SRGH VHU GHVSUH]tYHO GH WmR SHTXHQD $ YHORFLGDGH GH
VHGLPHQWDomRGHTXDOTXHUVROXWRSRGHVHUREWLGDDSDUWLUGDWD[DGHPRYLPHQWR
GH XP SRQWR QHVWD LQWHUIDFH FXMR UDLR rb  p GDGR SHOD (TXDo}HV   H

r
2 b
c p ra
r =r
b
2 2
p cr dr (5.36)

rp rb

r = r dc
b
2 2
dc (5.37)
ra ra

rp rp
dc dc
r = r
b
2
dr2
r dr dr (5.38)
ra
dr a

RQGH rp pRUDLRGHXPSRQWRQRSDWDPDU c p pDFRQFHQWUDomRQHVVHSRQWRHp ra 


RUDLRGRPHQLVFR$VGLIHUHQWHVIRUPDVGHH[SUHVVmRSDUD rb VmRHTXLYDOHQWHVPDV
VmR~WHLVSDUDVLVWHPDVySWLFRVGLIHUHQWHV

 7pFQLFDSDUD'HWHUPLQDomRGH3HVR0ROHFXODU3RQGHUDO0pGLR
)LJXUD3URFHVVRGHVHGLPHQWDomRHPXPDFpOXODGHXOWUDFHQWULIXJDomRVXEPHWLGDDURWDomR D 
9DULDomRGDFRQFHQWUDomRDRORQJRGDFpOXOD E *UDGLHQWHGHFRQFHQWUDomRREWLGRQDFpOXODFpD
FRQFHQWUDomRHUpDGLVWkQFLDDSDUWLUGRFHQWURGHURWDomR



0RQLWRUDQGR D FRQFHQWUDomR GXUDQWH R H[SHULPHQWR H FDOFXODQGR rb   R
FRHILFLHQWHGHVHGLPHQWDomR K sed pGDGRSHOD(TXDomRMiDSUHVHQWDGD
4XDQGR K sed pPHGLGRSHODV(TXDo}HVSDUDXPVROXWRKHWHURJrQHRR
YDORUREWLGRVHUiRFRHILFLHQWHGHVHGLPHQWDomRSRQGHUDOPpGLR K sed , w 
1RFDVRGHXPDVROXomRLGHDOKRPRJrQHDVHGLPHQWDQGRUDSLGDPHQWHDLQWHUIDFH
p TXDVH VLPpWULFD H rb  FRUUHVSRQGH GH PRGR DSUR[LPDGR DR UDLR QR TXDO D
FRQFHQWUDomRpDPHWDGHGRYDORUHQFRQWUDGRQRSDWDPDUEHPFRPRRUDLRQRTXDO
(dc / dr ) pPi[LPR3RUHVWDUD]mRpXPDSUiWLFDFRPXPDSUR[LPDU rb SRUHVVHV
YDORUHV (VWD DSUR[LPDomR HP JHUDO QmR p YiOLGD SDUD VROXWRV KHWHURJrQHRV
OHYDQGRDHUURV
S(VWLPDWLYDGHGLVWULEXLomRGHSHVRPROHFXODU3DUDSROtPHURVOLQHDUHVKRPyORJRV
VHP FRQVLGHUDU R YROXPH H[FOXtGR p SRVVtYHO HVFUHYHU XPD UHODomR FRP EDVH
HPStULFDHWHyULFDHQWUHRFRHILFLHQWHGHVHGLPHQWDomRHRSHVRPROHFXODUVRED
IRUPD
K sed = kM a (5.39)

&DUDFWHUL]DomRGH3ROtPHURV 
RQGH k H a VmRFRQVWDQWHVVREXPGDGRFRQMXQWRGHFRQGLo}HV8VDQGRIUDo}HVGH
SROtPHUR GH M  FRQKHFLGR SDUD XP GDGR SDU SROtPHURVROYHQWH D XPD GDGD
WHPSHUDWXUDpSRVVtYHOHVWDEHOHFHURVYDORUHVGH k H a (VWDDSUR[LPDomRpVLPLODU
jTXHODXVDGDSDUDQ~PHURGHYLVFRVLGDGHOLPLWHDTXDOQmRpXPPpWRGRDEVROXWR
1DWHPSHUDWXUD RH[SRHQWH a pDSUR[LPDGDPHQWH(VWDUHODomRWHPVLGR
XVDGDFRPREDVHGHYiULRVPpWRGRVVLPLODUHVGHREWHQomRGHGLVWULEXLomRGHSHVR
PROHFXODU f (M ) DSDUWLUGDGLVWULEXLomRGHFRHILFLHQWHVGHVHGLPHQWDomR6HYiULDV
IUDo}HV GR VROXWR GH GLIHUHQWHV SHVRV PROHFXODUHV HVWLYHUHP GLVSRQtYHLV HQWmR p
SRVVtYHO PHGLU M w  H K sed , w  SDUD FDGD XPD GHODV FRQVWUXLU D FXUYD GH log M w 
FRQWUD ORJ K sed , w  H REWHU HQWmR RV YDORUHV GH k  H a  $ UHSUHVHQWDomR JUiILFD
GHVHMDGD GH f (M ) FRQWUD M  p REWLGD GLUHWDPHQWH GD FXUYD GH g ( K sed )  HP
IXQomRGH K sed 
([SHULPHQWRVGHYHORFLGDGHGHVHGLPHQWDomRVmRXVDGRVSDUDYHULILFDUDSXUH]D
GHVROXWRVPDFURPROHFXODUHV(PVLVWHPDGHGRLVFRPSRQHQWHVFDGDFRPSRQHQWHp
UHVROYLGR QD IRUPD GH SLFRV 2V SLFRV LQGLYLGXDLV SRGHP HVWDU SDUFLDOPHQWH RX
FRPSOHWDPHQWHVHSDUDGRV$SUHVHQoDGHLPSXUH]DVSRGHVHUGHWHFWDGDPHVPRQD
IRUPD GH XP SHTXHQR RPEUR QR SLFR REWLGR (P XP VLVWHPD PDFURPROHFXODU R
DODUJDPHQWRGRSLFRSRGHVHUFRQVLGHUDGRXPDLQGLFDomRGHSROLGLVSHUVmR

Qual o efeito da concentrao sobre os resultados obtidos ?


2FRHILFLHQWHGHVHGLPHQWDomRGHFUHVFHFRPRDXPHQWRGDFRQFHQWUDomRGRVROXWR
'DtDDOWDVFRQFHQWUDo}HVDTXHODVPROpFXODVTXHHVWmRQRUDVWURGDLQWHUIDFHFRPR
UHVXOWDGR GD SROLGLVSHUVmR GD GLIXVmR PRYHPVH SDUD XPD UHJLmR GH EDL[D
FRQFHQWUDomR (VWDV PROpFXODV PRYHPVH PDLV UDSLGDPHQWH TXH DTXHODV QD UHJLmR
GRSDWDPDUHVmRFDSWXUDGDV&RQVHTXHQWHPHQWHRSLFRUHVXOWDQWHpPDLVHVWUHLWR
GRTXHRHVSHUDGR$OJXPDVYH]HVXPDLPSXUH]DFRPFRQVWDQWHGHVHGLPHQWDomR
OLJHLUDPHQWH PDLV EDL[D SRGH HVFDSDU j GHWHFomR (VWH HIHLWR SRGH VHU FRQWRUQDGR
SHORXVRGHFRQFHQWUDo}HVPDLVEDL[DV
3RURXWURODGRDFRQFHQWUDo}HVPXLWREDL[DVSRGHRFRUUHUFRQYHFomRQDFpOXOD
FRP FHUWD IDFLOLGDGH $ YLVFRVLGDGH GD PDLRULD GDV VROXo}HV HVWXGDGDV HP XPD
FHQWUtIXJDpEDL[D'RSRQWRGHYLVWDGDKLGURGLQkPLFDPDFURVFySLFDHVVDVVROXo}HV
SRGHP VH FRPSRUWDU FRPR IOXLGRV LGHDLV YLVFRVLGDGH LJXDO D ]HUR  8P IDWR EHP
FRQKHFLGR QD KLGURGLQkPLFD GH IOXLGRV LGHDLV p TXH XP YyUWLFH XPD YH] IRUPDGR
SHUPDQHFH SDUD VHPSUH RX SRU XP ORQJR WHPSR TXDQGR D YLVFRVLGDGH p EDL[D
SRUpP ILQLWD  2 YyUWLFH SRGH VHU IRUPDGR QD FpOXOD GD XOWUDFHQWUtIXJD GHYLGR D
LUUHJXODULGDGHV PHFkQLFDV EHP SHTXHQDV GR PRYLPHQWR GR URWRU (P JHUDO RV
URWRUHV PDLV SHVDGRV VmR PHQRV SURSHQVRV j IRUPDomR GH YyUWLFHV 2V YyUWLFHV
FDXVDP PLVWXUD GD VROXomR QD FpOXOD R TXH FRQWULEXL GH IRUPD QHJDWLYD SDUD R
SURFHVVR FHQWUtIXJR 0HVPR HP FRUULGDV PDLV VXDYHV GD XOWUDFHQWUtIXJD H[LVWHP

 7pFQLFDSDUD'HWHUPLQDomRGH3HVR0ROHFXODU3RQGHUDO0pGLR
RSRUWXQLGDGHV VXILFLHQWHV SDUD LQLFLDU XPD FRUULGD FRQYHFWLYD )HOL]PHQWH H[LVWH
XP HIHLWR TXH WUDEDOKD FRQWUD D IRUPDomR GR YyUWLFH TXH p XP JUDGLHQWH GH
GHQVLGDGH1DSUHVHQoDGHXPJUDGLHQWHGHGHQVLGDGHDFRQYHFomRID]FRPTXHR
OtTXLGR PDLV GHQVR SRVLFLRQHVH DFLPD GR PHQRV GHQVR R TXH YDL GH HQFRQWUR jV
UHJUDV GH HTXLOtEULR PHFkQLFR $VVLP RV JUDGLHQWHV GH GHQVLGDGH HVWDELOL]DP D
FRUULGDFRQWUDDVFRQYHFo}HV(QWUHWDQWRRJUDGLHQWHGHHVWDELOL]DomRWHPTXHVHU
JUDQGHRVXILFLHQWHSDUDSURSRUFLRQDURHIHLWRGHVHMDGR6REFRQGLo}HVFRPSDUiYHLV
FRUULGDVDEDL[DVYHORFLGDGHVVmRPDLVSURSHQVDVjFRQYHFomRGRTXHDTXHODVDDOWDV
YHORFLGDGHV

5.2.5 Equilbrio de sedimentao


7UDGLFLRQDOPHQWH H[SHULPHQWRV GH HTXLOtEULR GH VHGLPHQWDomR HUDP XVDGRV SDUD
PHGLGDVGHSHVRVPROHFXODUHV$DQiOLVHpUD]RDYHOPHQWHVLPSOHVSDUDVROXo}HVTXH
VmRWHUPRGLQDPLFDPHQWHLGHDLV$SDUWLUGHXPVLPSOHVH[SHULPHQWRGHHTXLOtEULR
SRGHP VHU REWLGRV R SHVR PROHFXODU SRQGHUDO PpGLR M w  H WDPEpP R SHVR
PROHFXODUFHQWUtIXJRPpGLR M z $UD]mRGH M z M w IRUQHFHDSROLGLVSHUVmRGD
DPRVWUD7HFQLFDPHQWHSDUDDDYDOLDomRGHVWHVH[SHULPHQWRVGHYHVHUFRQKHFLGDD
FRQFHQWUDomR GH HTXLOtEULR QR PHQLVFR GD FROXQD (VVD FRQFHQWUDomR SRGH VHU
HVWDEHOHFLGD SRU PHLR   GR XVR GD OHL GH FRQVHUYDomR GH PDVVD D SDUWLU GD
FRQFHQWUDomR RULJLQDO GD DPRVWUD RX   GD VHOHomR GH XPD YHORFLGDGH
VXILFLHQWHPHQWH DOWD GR URWRU FDSD] GH WRUQDU D FRQFHQWUDomR QR PHQLVFR WmR
SHTXHQD TXH SRVVD VHU GHVSUH]DGD 2 VHJXQGR PpWRGR p OLJHLUDPHQWH PHQRV
SUHFLVRPDVDSUHVHQWDDYDQWDJHPGHQmRUHTXHUHUXPH[SHULPHQWRVHSDUDGRSDUD
DPHGLGDGDFRQFHQWUDomRRULJLQDO
'XUDQWH R SURFHVVR GH VHGLPHQWDomR XPD DPRVWUD GH XP PDWHULDO
PDFURPROHFXODU SROLGLVSHUVR UHGLVWULEXLVH GHQWUR GD FpOXOD $V PROpFXODV PDLV
SHVDGDV VHGLPHQWDPVH PDLV UiSLGR H QR HTXLOtEULR HODV DVVHQWDPVH PDLV
SUy[LPDV DR IXQGR GD FpOXOD (VWD FDUDFWHUtVWLFD FRPSOLFD RV H[SHULPHQWRV
GLUHFLRQDGRV SDUD D REWHQomR GR SHVR PROHFXODU PpGLR (QWUHWDQWR WDO
UHGLVWULEXLomRFRQIHUHXPDRSRUWXQLGDGHSDUDHVWXGDUDSROLGLVSHUVmRGHDPRVWUDV
GHSROtPHUR$VLWXDomRpDLQGDPDLVFRPSOLFDGDSHODQmRLGHDOLGDGHGDVVROXo}HV
8PD DQiOLVH GHWDOKDGD UHTXHU PHGLGDV GH GLYHUVDV VROXo}HV FRP FRQFHQWUDo}HV
LQLFLDLVGHSROtPHURYDULDGDV3DUDFDGDVROXomRRHTXLOtEULRGHVHGLPHQWDomRGHYH
VHU HVWDEHOHFLGR SDUD GLIHUHQWHV YHORFLGDGHV GR URWRU 2 WUDEDOKR HQYROYLGR p
FRQVLGHUiYHO(QWUHWDQWRXPDDQiOLVHDSURSULDGDLUiIRUQHFHUWDQWRDGLVWULEXLomRGH
SHVRPROHFXODUTXDQWRRYDORUGRVHJXQGRFRHILFLHQWHGRYLULDO
1RV H[SHULPHQWRV GH HTXLOtEULR GH VHGLPHQWDomR D FRQGLomR SDUD R HTXLOtEULR
~  WHP TXH VHU FRQVWDQWH HP WRGDV DV SDUWHV GR
UHTXHU TXH R SRWHQFLDO WRWDO
VLVWHPD 3DUD XP SROtPHUR GH SHVR PROHFXODU M 2  GLVVROYLGRHPXPVROYHQWH  

&DUDFWHUL]DomRGH3ROtPHURV 
FRORFDGRVHPXPFDPSRFHQWUtIXJRGHYHORFLGDGHDQJXODU VXDHQHUJLDSRWHQFLDO
E p  D XPD GLVWkQFLD r  GR VHX FHQWUR GH URWDomR p GDGD SHOD (TXDomR  H VHX
SRWHQFLDOTXtPLFRp 
E p = M 2 2 r 2 / 2 (5.40)

2SRWHQFLDOWRWDOpHQWmRH[SUHVVRSHOD(TXDomR
~ = ( M 2 2 r 2 / 2) (5.41)

HDVFRQGLo}HVSDUDRHTXLOtEULRVmRGDGDVSHOD(TXDomR
~
= M 2 2 r = 0 (5.42)
r r
&RQVLGHUDQGR DJRUD R WUDQVSRUWH GH J  PROHV GH SROtPHUR HP XPD XQLGDGH GH
iUHDGHVHomRWUDQVYHUVDOQDXQLGDGHGHWHPSRDHTXDomRGHWUDQVSRUWHpGDGDSHOD
(TXDomR

J = L M 2 r (5.43)
r
RQGH L = c 2 / N A f  p D FRQGXWLYLGDGH PiVVLFD D TXDO p SURSRUFLRQDO j
FRQFHQWUDomRGDVXEVWkQFLDHLQYHUVDPHQWHSURSRUFLRQDOjUHVLVWrQFLDRIHUHFLGDSHOR
PHLRDRWUDQVSRUWHLVWRpRFRHILFLHQWHGHIULFomRSRUPRO f 
2 SRWHQFLDO TXtPLFR  p XPD IXQomR GH T  P  H c 2  PDV VH T  p FRQVWDQWH
HQWmR
P c
= + 2 (5.44)
r P T ,C r c 2 T , P r
HFRPR
P
= V2 = 2 M 2 ; = 2 r ;
P r

RT 2
= 1 + c 2 (5.45)
c 2 c2 c 2
RQGH 2 pRFRHILFLHQWHGHDWLYLGDGHGRVROXWR3DUDXPDVROXomRLGHDOWHPVHTXH
RT c 2
= M 2 2 r +
2
(5.46)

r c 2 r

 7pFQLFDSDUD'HWHUPLQDomRGH3HVR0ROHFXODU3RQGHUDO0pGLR
6XEVWLWXLQGRD(TXDomRQD(TXDomRREWpPVH
RT c 2
J = L M 2 2 2 r M 2 2 r + (5.47)
c 2 r
RX
RT c 2
J = L M 2 2 r (1 2 ) (5.48)
c 2 r
8VDQGR DV (TXDo}HV  H  H D GHILQLomR GH L  D (TXDomR  SRGH VHU
HVFULWDFRPR
J = K sed 2 rc2 D(c2 / r ) (5.49)

,VWR PRVWUD TXH R IOX[R J  p R UHVXOWDGR OtTXLGR GD WD[D GH VHGLPHQWDomR H GD
GLIXVmRGDVPROpFXODVHPGLUHomRFRQWUiULD1RHTXLOtEULRGHVWHEDODQoRQmRRFRUUH
IOX[RH J = 0 (QWmRVHJXHVHTXH
dc 2 rM 2 (1 2 )
2
1
= (5.50)
c2 dr RT
(VWDHTXDomRGHVFUHYHRJUDGLHQWHGHFRQFHQWUDomRQRHTXLOtEULRSDUDXPVROXWR
~QLFRVREFRQGLo}HVGHVROXomRLGHDOHDLQWHJUDomRHQWUHRPHQLVFR rm HTXDOTXHU
SRQWR r QDFpOXODGi
c(r ) 2 M 2 (1 2 )(r 2 rm2 )
ln = (5.51)
c(rm ) 2 RT
8P JUiILFR GH ln c(r )  HP IXQomR GH r 2  SRGH VHU FRQVWUXtGR PHGLQGRVH DV
FRQFHQWUDo}HVHPGLIHUHQWHVSRQWRVGDFpOXODH M 2 SRGHVHUFDOFXODGRDSDUWLUGD
LQFOLQDomR GD FXUYD 2 SULQFLSDO SUREOHPD H[SHULPHQWDO UHVLGH QD REWHQomR GD
FRQFHQWUDomRHPFDGDSRQWRGDFpOXODRTXHQmRpPXLWRVLPSOHV2PpWRGRPDLV
XVDGR FRQVLVWH QR FiOFXOR GD GLIHUHQoD GH FRQFHQWUDomR HQWUH DTXHOD GR PHQLVFR
> c(m ) @HDGRIXQGRGDFpOXOD> c(b ) @
5HDUUDQMDQGRHLQWHJUDQGRD(TXDomRREWpPVH
M 2 (1 2 ) 2
rb rb
dc
r dr dr = RT rc(r ) dr
rm
(5.52)
m

&RQVLGHUDQGR D FRQVHUYDomR GH PDVVD HP XPD SDUWH GD FpOXOD D (TXDomR 
SRGHVHUHVFULWDQDIRUPDGD(TXDomR

&DUDFWHUL]DomRGH3ROtPHURV 
M 2 (1 2 ) 2 (rb2 rm2 )co
c(b) c(m) = (5.53)
RT 2
RQGH c o pDFRQFHQWUDomRLQLFLDO
3DUDXPSROtPHURSROLGLVSHUVRHVWDHTXDomRIRUQHFHRSHVRPROHFXODUSRQGHUDO
PpGLR M w  2 SHVR PROHFXODU z  PpGLR M z  SRGH VHU FDOFXODGR D SDUWLU GH
JUDGLHQWHVGHFRQFHQWUDomRQRWRSRHQRIXQGRGDFpOXOD (TXDomR 
1 dc 1 dc
M z = RT (c(b) c(m))(1 2 )
2
(5.54)
rb drb rm drm
$ SULQFLSDO GHVYDQWDJHP QR PpWRGR UHVLGH QRV ORQJRV SHUtRGRV GH WHPSR
UHTXHULGRVSDUDVHDWLQJLURHTXLOtEULR
2 YDORU GH M w  FDOFXODGR GD (TXDomR  REYLDPHQWH p XP YDORU DSDUHQWH
UHODFLRQDGR j FRQFHQWUDomR LQLFLDO GD VROXomR VHQGR QHFHVViULR UHDOL]DU D
H[WUDSRODomRSDUDFRQFHQWUDomR]HUR

5.2.6 Observaes gerais


(PH[SHULPHQWRVGHHTXLOtEULRGHVHGLPHQWDomRRWHPSRUHTXHULGRSDUDDOFDQoDUR
HTXLOtEULRYDULDGHDOJXPDVKRUDVDWpDOJXQVGLDV,VVRGHSHQGHGRFRPSULPHQWRGD
FROXQDGDVROXomRGDYLVFRVLGDGHGDVROXomRHGRFRHILFLHQWHGHGLIXVmRGRVROXWR
1HVWH SURFHGLPHQWR WRUQDVH LPSRUWDQWH GHWHUPLQDU TXDQGR R HTXLOtEULR IRL
DOFDQoDGRHLVWRSRGHVHUUHDOL]DGRWRPDQGRVHIRWRJUDILDVRXUHJLVWURVHPWHPSRV
YDULDGRV DR ORQJR GR H[SHULPHQWR H FRPSDUDQGRRV HQWUH VL $ SDUWLU GD OHLWXUD
GHVVD YDUUHGXUD VmR FRUUHODFLRQDGRV GDGRV GH FRQFHQWUDomR ]HUR DUELWUiULR  HP
IXQomRGRUDLRRXGDGRVGHSULPHLUDGHULYDGDGDFRQFHQWUDomRHPIXQomRGRUDLRRX
DLQGDGDGRVGHFRQFHQWUDomRUHDOHPIXQomRGRUDLR6HRREMHWLYRIRUGHWHUPLQDU
SHVRPROHFXODUSRQGHUDOPpGLRDSDUWLUGHUHJLVWURVUHIUDWRPpWULFRVVHPXWLOL]DomR
GH XPD WpFQLFD GH DOWD YHORFLGDGH ID]VH QHFHVViULR GHWHUPLQDU D FRQFHQWUDomR
LQLFLDO GD VROXomR SRU PHLR GH XP H[SHULPHQWR SDUDOHOR RX FRP XP UHIUDW{PHWUR
GLIHUHQFLDO
2V H[SHULPHQWRV GH YHORFLGDGH GH VHGLPHQWDomR HP JHUDO VmR UHDOL]DGRV D
YHORFLGDGHV GH URWRU UHODWLYDPHQWH DOWDV GXUDQWH DOJXPDV KRUDV )RWRJUDILDV RX
YDUUHGXUDVVmRWRPDGDVDXWRPDWLFDPHQWHDLQWHUYDORVGHWHPSRFRQKHFLGRVDILP
GHVHJXLURSURJUHVVRGDLQWHUIDFHTXHpIRUPDGD2VUHVXOWDGRVH[SHULPHQWDLVVmR
REWLGRV QD IRUPD GH XPD VpULH GH TXDGURV GH FRQFHQWUDomR RX VHX JUDGLHQWH HP
IXQomRGRUDLRDXPDVHTrQFLDGHWHPSRV2VUHJLVWURVREWLGRVSRGHPVHUWUDWDGRV
GH GLYHUVRV PRGRV $WXDOPHQWH H[LVWHP GLYHUVRV SURJUDPDV GH FRPSXWDGRU
DSURSULDGRVSDUDRWUDWDPHQWRGRVGDGRVH[SHULPHQWDLV

 7pFQLFDSDUD'HWHUPLQDomRGH3HVR0ROHFXODU3RQGHUDO0pGLR
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7DJHU$3K\VLFDO&KHPLVWU\RI3RO\PHUV0,53XEOLVKHUV0RVFRZ
9ROOPHUW%3RO\PHU&KHPLVWU\6SULQJHU9HUODJ%HUOLQ
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&DUDFWHUL]DomRGH3ROtPHURV 
&DStWXOR

Viscosimetria

6.1 Definio de viscosidade


)OX[RpRGHVORFDPHQWRLUUHFXSHUiYHOGHXPDVPROpFXODV GHXPDGDGDVXEVWkQFLD 
HP UHODomR jV RXWUDV VRE D DomR GH XPD WHQVmR H[WHUQD ,PDJLQHPRV XP IOXLGR
HVFRDQGRDWUDYpVGHXPWXERFDSLODUFRPRHVTXHPDWL]DGRQD)LJXUD(VWHIOXLGR
SRGHVHUXPDVXEVWkQFLDGHEDL[RSHVRPROHFXODUXPSROtPHURQRHVWDGRIXQGLGR
RX XPD VROXomR GH SROtPHUR ,PDJLQHPRV DLQGD HVWH PHVPR IOXLGR GLYLGLGR
DUELWUDULDPHQWH HP FDPDGDV FRQFrQWULFDV p IiFLO FRQFOXLU TXH HVWDV FDPDGDV TXH
FRQVWLWXHPRIOXLGRPRYHPVHFRPYHORFLGDGHVGLIHUHQWHV$YHORFLGDGHQRLQWHULRU
GR WXER p EHP PDLRU GR TXH DTXHOD SUy[LPD j SDUHGH GR WXER GHYLGR DR DWULWR
HQWUH R IOXLGR H D SDUHGH 1D GLUHomR SHUSHQGLFXODU DR IOX[R H[LVWH HQWmR XP
GHWHUPLQDGR JUDGLHQWH GH YHORFLGDGH v r  RQGH Y p D YHORFLGDGH GH
HVFRDPHQWRHUpRUDLRGRFtUFXORFRQFrQWULFRFRUUHVSRQGHQWH

)LJXUD(VTXHPDGHXPIOXLGRHVFRDQGRHPXPWXERFDSLODU

'XUDQWHRHVFRDPHQWRDVPROpFXODVTXHHVWmRH[SRVWDVDGLIHUHQWHVYHORFLGDGHV
FROLGHP HQWUH VL JHUDQGR XPD WURFD GH PRPHQWR HQWUH DV FDPDGDV GR IOX[R (VWH

&DUDFWHUL]DomRGH3ROtPHURV 
IHQ{PHQR FDXVD XPD IULFomR LQWHUQD GLILFXOWDQGR R HVFRDPHQWR 1R FDVR GRV
SROtPHURVDIULFomRLQWHUQDHSRUWDQWRDUHVLVWrQFLDDRHVFRDPHQWRpPXLWRPDLRU
GHYLGR DR WDPDQKR GDV FDGHLDV H DR HQRYHODPHQWR HQWUH HODV (VWD UHVLVWrQFLD DR
HVFRDPHQWRFDXVDGDSHODIULFomRLQWHUQDpFRQKHFLGDFRPRYLVFRVLGDGH
$ YLVFRVLGDGH RX UHVLVWrQFLD DR HVFRDPHQWR SRGH RX QmR GHSHQGHU GD WHQVmR
DSOLFDGD WHQVmRGHFLVDOKDPHQWR HGDYHORFLGDGHGHFLVDOKDPHQWR6HDYLVFRVLGDGH
LQGHSHQGH GDV FRQGLo}HV GH GHIRUPDomR R IOXLGR p FKDPDGR QHZWRQLDQR 6H SRU
RXWUR ODGR D YLVFRVLGDGH YDULD FRP D YHORFLGDGH H WHQVmR GH FLVDOKDPHQWR GL]VH
TXHRVLVWHPDDSUHVHQWDFRPSRUWDPHQWRGHXPIOXLGRQmRQHZWRQLDQR
4XDQGR XPD WHQVmR p DSOLFDGD D XP IOXLGR FRQVWLWXtGR SRU PDFURPROpFXODV DV
FDGHLDV SROLPpULFDV HVWLFDPVH GH IRUPD D VH RULHQWDU QR IOX[R (VWD RULHQWDomR p
HQWUHWDQWR SHUWXUEDGD SHOD PRELOLGDGH WpUPLFD GDV FDGHLDV 4XDQWR PDLRU IRU D
PRELOLGDGHWpUPLFDPDLRUVHUiRQ~PHURGHFROLV}HVHQWUHDVFDGHLDVHPDLRUVHUiD
UHVLVWrQFLD DR IOX[R RX VHMD PDLRU VHUi D YLVFRVLGDGH $XPHQWDQGR D WHQVmR RX D
YHORFLGDGH DSOLFDGD DR VLVWHPD R JUDX GH RULHQWDomR GDV FDGHLDV DXPHQWDUi
GLPLQXLQGRRHIHLWRGDPRELOLGDGHWpUPLFDHFRQVHTXHQWHPHQWHDYLVFRVLGDGHVHUi
PHQRU 4XDQGR VH DXPHQWD PXLWR D WHQVmR GH FLVDOKDPHQWR D FRQIRUPDomR GDV
FDGHLDVDWLQJHXPPi[LPRGHRULHQWDomR$SDUWLUGHVWHSRQWRDYLVFRVLGDGHDWLQJH
R VHX PtQLPR QmR VHQGR PDLV LQIOXHQFLDGD SHOR DXPHQWR GD WHQVmR GH
FLVDOKDPHQWR$)LJXUDDSUHVHQWDXPDFXUYDWtSLFDTXHGHVFUHYHDGHSHQGrQFLD
GDYLVFRVLGDGHFRPDWHQVmRGHFLVDOKDPHQWR2SULPHLURSDWDPDU $ FRUUHVSRQGHj
YLVFRVLGDGH QHZWRQLDQD LQLFLDO H R VHJXQGR SDWDPDU %  FRUUHVSRQGH j YLVFRVLGDGH
QHZWRQLDQD PtQLPD $ SRUomR QR PHLR GD FXUYD &  FRUUHVSRQGH j YLVFRVLGDGH
HVWUXWXUDOHGHSHQGHGDVFRQGLo}HVGHGHIRUPDomR
$YLVFRVLGDGHGHXPVLVWHPDSROLPpULFRGHSHQGHGHYiULRVIDWRUHVWDLVFRPR
SSHVRPROHFXODUGRSROtPHUR
SWHQVmRHYHORFLGDGHGHFLVDOKDPHQWR
SWHPSHUDWXUD
SQDWXUH]DGRVROYHQWHQRFDVRGHVROXo}HVGHSROtPHUR

 9LVFRVLPHWULD
)LJXUD'HSHQGrQFLDGDYLVFRVLGDGHFRPDWHQVmRGHFLVDOKDPHQWR

4XDQGR VH WUDEDOKD FRP VROXo}HV GH SROtPHURV D FRQWULEXLomR GR JUDX GH
RULHQWDomRSDUDDYLVFRVLGDGHGLPLQXLFRQVLGHUDYHOPHQWHFRPDGLOXLomR2HIHLWRGD
PRELOLGDGH WpUPLFD QD YLVFRVLGDGH WRUQDVH PDLV LPSRUWDQWH ,VWR VLJQLILFD TXH R
HIHLWRGDWHQVmRHYHORFLGDGHGHFLVDOKDPHQWRpEHPPHQRUHPVROXo}HVGLOXtGDVGH
SROtPHURVHRVLVWHPDFRPSRUWDVHFRPRXPIOXLGRQHZWRQLDQR(VWDVFRQGLo}HVGH
EDL[D WHQVmR H EDL[D YHORFLGDGH GH FLVDOKDPHQWR VmR QHFHVViULDV SDUD D
GHWHUPLQDomRGDYLVFRVLGDGHOLPLWHGRIOXLGRGHQRPLQDGDYLVFRVLGDGHLQWUtQVHFD

6.2 Viscosidade de solues diludas de polmeros


2 HVWXGR GD YLVFRVLGDGH GH VROXo}HV VHULD EHP PDLV VLPSOHV VH R FRHILFLHQWH GH
YLVFRVLGDGHGDVROXomRIRVVHDVRPDGDVYLVFRVLGDGHVSDUFLDLVGHFDGDFRPSRQHQWH
QDVROXomR1DSUiWLFDHVWDUHODomRQmRVHDSOLFD
4XDQGR XPD PROpFXOD SHTXHQD p GLVVROYLGD HP XP VROYHQWH D YLVFRVLGDGH GR
VLVWHPDYDULDXPSRXFR1RFDVRGHPDFURPROpFXODVDFDGHLDSRVVXLXPWDPDQKR
PXLWRPDLRUHDVVXPHFRQIRUPDo}HVYDULDGDVFRPRVHUiYLVWRSRVWHULRUPHQWH&DGD
VHJPHQWRGHVWDFDGHLDSRGHHVWDUVREDDomRGHYHORFLGDGHVGHIOX[RGLIHUHQWHV,VWR
DFDUUHWDXPDXPHQWRVLJQLILFDWLYRGDYLVFRVLGDGHPHVPRHPVROXo}HVGLOXtGDV

6.2.1 Viscosidade real


$YLVFRVLGDGHGHXPIOXLGRHVFRDQGRDWUDYpVGHXPFDSLODUpIRUQHFLGDSHOD(TXDomR
GH3RLVHXLOOHDSUHVHQWDGDDVHJXLU

&DUDFWHUL]DomRGH3ROtPHURV 
V pr 4
= (6.1)
t 8 l
RQGH9WpRYROXPHHPFPGRIOXLGRHVFRDQGRDWUDYpVGRFDSLODUSRUXQLGDGHGH
WHPSRHPVHJXQGRSpDSUHVVmRKLGURVWiWLFDQRQtYHOGRIOXLGRHPGLQDFPUpR
UDLR GR FDSLODU HP FP O p R FRPSULPHQWR GR FDSLODU HP FHQWtPHWUR H  p D
YLVFRVLGDGHGRIOXLGRHPSRLVH
&RPR QRUPDOPHQWH VH WUDEDOKD FRP YROXPH FRQVWDQWH D (TXDomR  SRGH VHU
H[SUHVVDFRPR

.p.r 4
= t (6.2)
8lV
RQGH S p D GLIHUHQoD GH SUHVVmR HQWUH DV H[WUHPLGDGHV GR FDSLODU U p R UDLR GR
FDSLODU9pRYROXPHGRFRPSDUWLPHQWRTXHFRQWpPDVROXomROpRFRPSULPHQWR
GRFDSLODUHWpRWHPSRGHIOX[RDWUDYpVGRFDSLODU
(VWDUHODomRpYiOLGDTXDQGRRFRPSULPHQWRGRFDSLODUpPXLWRPDLRUGRTXHR
UDLRGRFDSLODU
6HROtTXLGRHVFRDVREDDomRGDJUDYLGDGHHQWmR

p = g.H . (6.3)
RQGHJpDDFHOHUDomRGDJUDYLGDGH+pDGLIHUHQoDGHQtYHOGROLTXLGRQRVEUDoRVGR
YLVFRVtPHWURHpDGHQVLGDGHUHODWLYDGROtTXLGR(QWmR

.g.H ..r 4
= t (6.4)
8.l.V
$(TXDomRFRUUHVSRQGHjYLVFRVLGDGHDEVROXWDGHXPOtTXLGRRXVROXomR&RPR
ROtTXLGRHVFRDDWUDYpVGHXPFDSLODU+pYDULiYHOHRSHVRGDFROXQDGROtTXLGRQR
FDSLODU WDPEpP VH DOWHUD 3DUD D REWHQomR GH UHVXOWDGRV SUHFLVRV XWLOL]DPVH
YLVFRVtPHWURVHVSHFLDOPHQWHFRQVWUXtGRVGHPRGRDPDQWHUFRQVWDQWHRYROXPHGR
OtTXLGRQRFDSLODU
&RPRDVPHGLGDVVmRUHDOL]DGDVVHPSUHHPXPPHVPRYLVFRVtPHWURHQWmR9O
H U VmR FRQVWDQWHV H D FROXQD GR OtTXLGR WDPEpP $ (TXDomR  SRGH HQWmR VHU
H[SUHVVDGHXPDIRUPDEHPPDLVVLPSOLILFDGD

= K ..t (6.5)
RQGH. +UJO9 

 9LVFRVLPHWULD
.pFRQKHFLGDFRPRFRQVWDQWHYLVFRVLPpWULFDHSRGHVHUGHWHUPLQDGDDSDUWLUGR
WHPSR GH HVFRDPHQWR GH XP OtTXLGR GH YLVFRVLGDGH FRQKHFLGD OtTXLGR SDGUmR 
XVDQGRXPGHWHUPLQDGRYLVFRVtPHWUR
$V(TXDo}HVHFRQVLGHUDPTXHRIOX[RpODPLQDUFRPYHORFLGDGHWHQGHQGR
D]HURQDVSDUHGHVGRFDSLODUHTXHROtTXLGRpLQFRPSUHVVtYHO(VWDVFRQVLGHUDo}HV
VmRYiOLGDVSDUDVROXo}HVGLOXtGDV

6.2.2 Viscosidade relativa


1R HVWXGR GH VROXo}HV GLOXtGDV GH SROtPHURV p PXLWR FRPXP GHWHUPLQDU D
YLVFRVLGDGHGDVROXomRHPUHODomRDRVROYHQWHSXUR$UHODomRHQWUHDYLVFRVLGDGHGD
VROXomR H D GR VROYHQWH SXUR p GHQRPLQDGD YLVFRVLGDGH UHODWLYD 3DUD GHWHUPLQDU R
YDORUGHVWDYLVFRVLGDGHRWHPSRGHHVFRDPHQWRGRVROYHQWHWHGDVROXomRWVmR
PHGLGRV QR PHVPR YLVFRVtPHWUR &RQVLGHUDQGR TXH D GHQVLGDGH GH VROXo}HV
GLOXtGDV p SUDWLFDPHQWH LJXDO j GR VROYHQWH SXUR D YLVFRVLGDGH UHODWLYD SRGH VHU
GHILQLGDFRPRDUD]mRHQWUHRWHPSRGHHVFRDPHQWRGDVROXomRHGRVROYHQWHSXUR
$ YLVFRVLGDGH HVSHFtILFD p GHILQLGD FRPR D UD]mR HQWUH D GLIHUHQoD GRV WHPSRV GH
HVFRDPHQWR GD VROXomR H GR VROYHQWH SXUR WW  H R WHPSR GH HVFRDPHQWR GR
VROYHQWHSXURW$PEDVVmRDGLPHQVLRQDLV$UHODomRHQWUHDYLVFRVLGDGHHVSHFtILFD
HDFRQFHQWUDomRGDVROXomRpGHQRPLQDGDYLVFRVLGDGHUHGX]LGD)LQDOPHQWHDUD]mR
HQWUH R ORJDULWPR GD YLVFRVLGDGH UHODWLYD H D FRQFHQWUDomR p FRQKHFLGD FRPR
YLVFRVLGDGHLQHUHQWH$7DEHODUHVXPHHVWDVGHILQLo}HVGHYLVFRVLGDGH
7DEHOD'HILQLo}HVGHWLSRVGHYLVFRVLGDGHHVXDVUHVSHFWLYDVUHODo}HV

1RPH (TXDomRTXHGHILQH 8QLGDGH


9LVFRVLGDGH
UHODWLYD
r = t t (6.6) DGLPHQVLRQDO
o

9LVFRVLGDGH t to
HVSHFtILFD
sp = r 1 = (6.7) DGLPHQVLRQDO
to
9LVFRVLGDGH sp
red = (6.8) G/J
UHGX]LGD c
9LVFRVLGDGH ln r
inh = (6.9) G/J
LQHUHQWH c

2VYDORUHVGHYLVFRVLGDGHUHODWLYDHVSHFtILFDUHGX]LGDHLQHUHQWHYDULDPFRPD
FRQFHQWUDomRGDVROXomR

&DUDFWHUL]DomRGH3ROtPHURV 
6.2.3 Viscosidade intrnseca

3DUD D GHWHUPLQDomR GD YLVFRVLGDGH LQWUtQVHFD RX Q~PHUR GH YLVFRVLGDGH OLPLWH p
QHFHVViULRGHWHUPLQDUDYLVFRVLGDGHUHGX]LGDRXLQHUHQWHDYiULDVFRQFHQWUDo}HVH
H[WUDSRODU j FRQFHQWUDomR ]HUR $ YLVFRVLGDGH LQWUtQVHFD SRGH HQWmR VHU GHILQLGD
FRPR

sp ln r
[ ]= clim

0 c
= lim
c0
(6.10)

c
$ YLVFRVLGDGH LQWUtQVHFD LQGHSHQGH GD FRQFHQWUDomR GD VROXomR &RPR DV
YLVFRVLGDGHV UHODWLYD H HVSHFtILFD VmR DGLPHQVLRQDLV D YLVFRVLGDGH LQWUtQVHFD WHP
FRPRXQLGDGHDUHFtSURFDGDFRQFHQWUDomRRXVHMDG/J
9iULDVHTXDo}HVHPStULFDVXVDGDVSDUDDGHWHUPLQDomRGDYLVFRVLGDGHLQWUtQVHFD
WrPVLGRGHVHQYROYLGDV$OJXQVH[HPSORVVmRIRUQHFLGRVDVHJXLU

Equao de Huggins

sp
= [] + K [] c
2
(6.11)
c
Equao de Kraemer

ln r
= [ ] + K [ ] c
2
(6.12)
c
Equao de Shulz-Blaschke

sp
= [ ] + K []sp (6.13)
c

 9LVFRVLPHWULD
Equao de Martin

sp
log = log[]+ K []c (6.14)
c
.L .LL .LLL H .LY VmR FRQVWDQWHV SDUD XP GHWHUPLQDGR SROtPHUR D XPD GHWHUPLQDGD
WHPSHUDWXUDHVROYHQWH
$)LJXUDLOXVWUDUHSUHVHQWDo}HVJUiILFDVGDV(TXDo}HVGH+XJJLQVH.UDHPHU
$PEDV DV UHWDV IRUQHFHP XP ~QLFR LQWHUFHSWR TXH FRUUHVSRQGH j YLVFRVLGDGH
LQWUtQVHFDRXVHMDDYLVFRVLGDGHjFRQFHQWUDomR]HUR
2 YDORU GD FRQVWDQWH GH +XJJLQV.L VLWXDVH QRUPDOPHQWH HP XPD IDL[D HQWUH
HHDXPHQWDTXDQGRRSRGHUGRVROYHQWHGHFUHVFH3DUDXPGHWHUPLQDGRSDU
SROtPHURVROYHQWHHVWDFRQVWDQWHQmRpHPJHUDOVHQVtYHODRSHVRPROHFXODU

)LJXUD5HSUHVHQWDomRJUiILFDGDYLVFRVLGDGHLQWUtQVHFD

4XDQGR D FRQVWDQWH GH .UDHPHU .L IRU PDLRU GR TXH  D (TXDomR
FRUUHVSRQGHQWHQmRIRUQHFHYDORUHVFRQILiYHLV1HVWHVFDVRVD(TXDomRGH+XJJLQV
pPDLVLQGLFDGD
4XDQGRDGHSHQGrQFLDGDYLVFRVLGDGHUHGX]LGDFRPDFRQFHQWUDomR (TXDomRGH
+XJJLQV DSUHVHQWDFXUYDWXUDFRQVLGHUiYHODH[WUDSRODomRjGLOXLomRLQILQLWDWRUQD
VHGLItFLOHSDUDHVWHFDVRD(TXDomRGH0DUWLQpPXLWRXVDGD

&DUDFWHUL]DomRGH3ROtPHURV 
$YLVFRVLGDGHLQWUtQVHFDSRGHVHUGHWHUPLQDGDDSDUWLUGHPHGLGDVGHYLVFRVLGDGH
DXPD~QLFDFRQFHQWUDomR(VWHWLSRGHGHWHUPLQDomRpFRQKHFLGRFRPRPpWRGRGH
XPSRQWRHpXWLOL]DGRTXDQGRDVFRQVWDQWHVGDVHTXDo}HVDFLPDIRUHPFRQKHFLGDV
(VWH PpWRGR Vy p YiOLGR TXDQGR D GHSHQGrQFLD HQWUH D YLVFRVLGDGH UHGX]LGD RX
LQHUHQWHFRPDFRQFHQWUDomRIRUOLQHDU

6.3 Mecanismo de fluxo de solues diludas de polmeros


6ROXo}HV SROLPpULFDV SRVVXHP YLVFRVLGDGH DOWD $ QDWXUH]D GD YLVFRVLGDGH GH
VROXo}HVSROLPpULFDVEDVHLDVHQRFRPSRUWDPHQWRGDVPDFURPROpFXODVHPVROXomR
RX VHMD QDV VXDV SURSULHGDGHV KLGURGLQkPLFDV $V SURSULHGDGHV KLGURGLQkPLFDV
HVWmRUHODFLRQDGDVDRPRYLPHQWRGDPDFURPROpFXODHPVROXomR
7RGD PROpFXOD HP VROXomR PRYLPHQWDVH GH PRGR WUDQVODFLRQDO H URWDFLRQDO 2
PRYLPHQWR WUDQVODFLRQDO GDV PDFURPROpFXODV UHODWLYR jV PROpFXODV GR VROYHQWH
SRGHVHUGRWLSR
SPRYLPHQWRDRDFDVR PRYLPHQWR%URZQLDQR 
SPRYLPHQWRGLUHFLRQDGR SRUGLIXVmR 
SPRYLPHQWRHPXPFDPSRFHQWUtIXJR SRUVHGLPHQWDomR 

4XDQGRXPDPDFURPROpFXODHVWiVREDDomRGHXPIOX[RODPLQDU )LJXUD D


XPDYHORFLGDGHGHFLVDOKDPHQWRGHILQLGDRVGLIHUHQWHVVHJPHQWRVGHVWDPDFURPR
OpFXOD PRYHPVH D YHORFLGDGHV GLIHUHQWHV ,VWR RFRUUH GHYLGR DR JUDGLHQWH GH
YHORFLGDGH SUHVHQWH HP XP IOX[R ODPLQDU FRPR H[SOLFDGR DQWHULRUPHQWH $
PDFURPROpFXOD GHYLGR DR VHX DOWR WDPDQKR PROHFXODU SRVVXL VHJPHQWRV ORFDOL
]DGRVHP]RQDVGHHVFRDPHQWRGHYHORFLGDGHVYDULDGDV$LQIOXrQFLDGRIOX[RPDLV
UiSLGRRXPHQRVUiSLGRHPXPDPDFURPROpFXODSURYRFDPRYLPHQWRVGHURWDomR
2V PRYLPHQWRV URWDFLRQDO H WUDQVODFLRQDO GDV PDFURPROpFXODV FDXVDP DWULWR
HQWUH RV VHXV VHJPHQWRV H DV PROpFXODVGRVROYHQWH,VWRSURYRFDXPDXPHQWRGD
YLVFRVLGDGHGRVLVWHPDHPUHODomRDRVROYHQWHSXUR
$ YLVFRVLGDGH LQWUtQVHFD >@ p GHILQLGD FRPR D YLVFRVLGDGH j FRQFHQWUDomR
LQILQLWDPHQWH GLOXtGD WHQGHQGR D ]HUR (VWD YLVFRVLGDGH p UHODFLRQDGD DSHQDV DR
PRYLPHQWRURWDFLRQDOGHXPDPDFURPROpFXODLQGLYLGXDO
(PVROXo}HVGLOXtGDVXPDPDFURPROpFXODORQJDHIOH[tYHODVVXPHDIRUPDGHXP
QRYHOR ([LVWHP GXDV WHRULDV EiVLFDV D UHVSHLWR GR FRPSRUWDPHQWR GHVWH QRYHOR
GXUDQWHRHVFRDPHQWR

Primeira teoria: modelo da partcula solvatada


'XUDQWHRIOX[RRVROYHQWHSDVVDOLYUHPHQWHDWUDYpVGRQRYHOR,VWRVLJQLILFDTXHR
PRYLPHQWR GR PHLR LQGHSHQGH GR PRYLPHQWR GRV VHJPHQWRV GR QRYHOR RX VHMD

 9LVFRVLPHWULD
FDGD VHJPHQWR VRIUH R PHVPR DWULWR QR PHLR TXH R FLUFXQGD FRPR VRIUHULD QD
DXVrQFLDGHRXWURVVHJPHQWRVGDPDFURPROpFXOD

Segunda teoria: modelo da partcula macia


$ PDFURPROpFXOD QD IRUPD GH XP QRYHOR UHWpP XPD TXDQWLGDGH GHILQLGD GH
VROYHQWH4XDQGRHODHVWiVREDDomRGHXPIOX[RHODPRYHVHMXQWRFRPDSRUomR
GH VROYHQWH FDSWXUDGD GHQWUR GHVWH QRYHOR 'H DFRUGR FRP HVWH PRGHOR R QRYHOR
PDFURPROHFXODUpFRQVLGHUDGRHVIpULFRFRPUDLRHIHWLYR5HIIFRUUHVSRQGHQWHDRUDLR
GDHVIHUDLQFKDGDFRPRVROYHQWH&RPRRQRYHORPDFURPROHFXODUpFRQVWLWXtGRQD
YHUGDGHGHXPDPROpFXODGHSROtPHURHGDSRUomRGHVROYHQWHLQFOXVDRFRQMXQWR
SRGHVHUFRQVLGHUDGRXPDSDUWtFXODPDFLoDVHQGRLPSHUPHiYHODRUHVWRGRVROYHQWH
GRVLVWHPD
3DUWtFXODV HVIpULFDV TXH QmR LQWHUDJHP FRP R VROYHQWH DSUHVHQWDP XPD
YLVFRVLGDGHHVSHFtILFDGHDFRUGRFRPDVHJXLQWHHTXDomRGHVHQYROYLGDSRU(LQVWHLQ

= 2,5 (6.15)
RQGHpDIUDomRYROXPpWULFDGDVSDUWtFXODVHVIpULFDV
3RGHVH DVVXPLU HQWmR TXH VRE D DomR GH XP FDPSR FLVDOKDQWH R QRYHOR
SROLPpULFR FRQWHQGR R VROYHQWH QR VHX LQWHULRU FRPSRUWDVH FRPR XPD HVIHUD GH
(LQVWHLQ
$ IUDomR YROXPpWULFD GDV SDUWtFXODV HVIpULFDV p LJXDODUD]mRHQWUHRYROXPHGD
SDUWtFXODHVIpULFDYHRYROXPHGDVROXomR96DEHQGRVHTXH
SRYROXPHGHVWDHVIHUDFRUUHVSRQGHD5H
SR UDLR GHVWD HVIHUD p QD YHUGDGH R UDLR HIHWLYR 5HII TXH HQJORED R QRYHOR H R
VROYHQWHLQFOXVR
HQWmRDYLVFRVLGDGHHVSHFtILFDSRGHVHUGHILQLGDSHOD(TXDomR

n.4 3 .Reff
3
sp = 2,5 (6.16)
V
RQGHQpRQ~PHURGHSDUWtFXODVHVIpULFDV
$UD]mRHQWUHRQ~PHURGHSDUWtFXODVHVIpULFDVHRQ~PHURGH$YRJDGURIRUQHFH
RQ~PHURGHPROHVGRSROtPHURGHDFRUGRFRPDVHJXLQWHHTXDomR

n m m.N A
= RX n= (6.17)
NA M M

&DUDFWHUL]DomRGH3ROtPHURV 
RQGHPpDPDVVDGRSROtPHURHPJUDPDH0pRVHXSHVRPROHFXODU6XEVWLWXLQGRR
Q~PHUR GH SDUWtFXODV Q GD (TXDomR  SHOD (TXDomR  D YLVFRVLGDGH
HVSHFtILFDSRGHVHUGHILQLGDFRPR

m.N A 4 3
sp = 2,5 . Reff (6.18)
M .V 3
&RPRP9pDFRQFHQWUDomRGDVROXomRHPJP/SRGHVHFRQFOXLUTXH

sp N
= 2,5 A . 4 R3 (6.19)
c M 3 eff
([WUDSRODQGRjFRQFHQWUDomR]HURREWpPVHDYLVFRVLGDGHLQWUtQVHFDHPUHODomR
DR UDLR HIHWLYR GD HVIHUD H DR SHVR PROHFXODU GR SROtPHUR FRPR GHPRQVWUD D
(TXDomR

sp 3
Reff
[] = lim c M (6.20)

c 0
&RQVLGHUDQGR D (TXDomR  SRGHVH FRQFOXLU TXH D YLVFRVLGDGH LQWUtQVHFD p
SURSRUFLRQDO DR YROXPH KLGURGLQkPLFR HIHWLYR GD PDFURPROpFXOD HP VROXomR H
LQYHUVDPHQWH SURSRUFLRQDO DR SHVR PROHFXODU GD PDFURPROpFXOD 6H R UDLR HIHWLYR
GR QRYHOR IRU FRQVLGHUDGR SURSRUFLRQDO j UDL] TXDGUDGD GR SHVR PROHFXODU GR
SROtPHURDYLVFRVLGDGHLQWUtQVHFDSRGHVHUH[SUHVVDFRPR

sp
[] = lim c
( M ) 3

= M (6.21)
c 0 M

6.4 Determinao do peso molecular viscosimtrico mdio


$VGHSHQGrQFLDVGDYLVFRVLGDGHLQWUtQVHFDFRPRSHVRPROHFXODUGRSROtPHURTXH
DFDEDPRV GH GLVFXWLU VmR EDVHDGDV HP PRGHORV WHyULFRV ([SHULPHQWDOPHQWH RV
YDORUHVGHYLVFRVLGDGHLQWUtQVHFDHQFRQWUDPVHQDPDLRULDGRVFDVRVHQWUHRVGRLV
PRGHORV
$ YLVFRVLGDGH LQWUtQVHFD p UHODFLRQDGD DR SHVR PROHFXODU SRU PHLR GD HTXDomR
FRQKHFLGDFRPRHTXDomRGH0DUN.XKQ+RXZLQN6DNXUDGDGHVFULWDDVHJXLU

 9LVFRVLPHWULD
[] = K. M a (6.22)
(VWD HTXDomR p PXLWR XVDGD SDUD D GHWHUPLQDomR GR SHVR PROHFXODU GH XP
SROtPHUR 2V YDORUHV GH . H D VmR FRQVWDQWHV SDUD XP GHWHUPLQDGR SDU SROtPHUR
VROYHQWHHSDUDXPDGHWHUPLQDGDWHPSHUDWXUD
1DPDLRULDGRVFDVRVDVLWXDVHHQWUHH3DUDSROtPHURVPHQRVIOH[tYHLV
REVHUYDPVH PDLRUHV YDORUHV GH D 3RGHVH HQWmR FRQFOXLU TXH RV YDORUHV GH D
IRUQHFHPXPDLGpLDDUHVSHLWRGDFRQIRUPDomRGDPDFURPROpFXODHPVROXomR
$ GLVFUHSkQFLD HQWUH DV UHODo}HV WHyULFDV H H[SHULPHQWDLV GH YLVFRVLGDGH
LQWUtQVHFDHSHVRPROHFXODUpH[SOLFDGDSHORHIHLWRGRYROXPHH[FOXtGRGLVFXWLGRQR
FDStWXOR  2V FiOFXORV WHyULFRV QmR OHYDP HP FRQVLGHUDomR DV LQWHUDo}HV GH ORQJD
GLVWkQFLDQHPDH[SDQVmRGRQRYHORGHYLGRjVLQWHUDo}HVSROtPHURVROYHQWH'HYLGR
DHVWDVLQWHUDo}HVRQRYHORPDFURPROHFXODUHPVROXomRSRGHDVVXPLUXPWDPDQKR
 YH]HV PDLRU GR TXH R LGHDO e LPSRUWDQWH OHPEUDU TXH R IDWRU  UHIHUHVH DR
FRHILFLHQWH GH H[SDQVmR GR QRYHOR QD SUHVHQoD GH XP ERP VROYHQWH &DS  
&RQVLGHUDQGR D LQIOXrQFLD GR FRHILFLHQWH GH H[SDQVmR D HTXDomR TXH UHODFLRQD D
YLVFRVLGDGHFRPRSHVRPROHFXODUSRGHVHUGHVFULWDFRPR

[] =
1
K. . M 2
3 (6.23)
6H DV PHGLGDV GH YLVFRVLGDGH IRUHP UHDOL]DGDV HP XP VROYHQWH LGHDO R
FRHILFLHQWH GH H[SDQVmR  p LJXDO j XQLGDGH $ GHSHQGrQFLD GD YLVFRVLGDGH FRP R
SHVR PROHFXODU VHJXH HQWmR R PRGHOR GD HVIHUD PDFLoD H[SUHVVD SHOD (TXDomR

$ (TXDomR GH 0DUN+RXZLQN (TXDomR   IRUQHFH R SHVR PROHFXODU
YLVFRVLPpWULFRPpGLRGHILQLGRSHOD(TXDomR
1
N M 1+ a a
1
i i
M V = wi M ia = i =1
a
i =1 (6.24)

Ni M i
i =1
2VYDORUHVGH.HDGD(TXDomRSRGHPVHUGHWHUPLQDGRVH[SHULPHQWDOPHQWH
XWLOL]DQGRVHXPDVpULHKRPyORJDGHSROtPHURVPRQRGLVSHUVRVTXHGLIHUHPDSHQDV
QRSHVRPROHFXODU$VYLVFRVLGDGHVLQWUtQVHFDVGHVWHVSROtPHURVVmRGHWHUPLQDGDVH
UHODFLRQDGDV DR VHX UHVSHFWLYR SHVR PROHFXODU SRU PHLR GR ORJDULWPR GD (TXDomR

&DUDFWHUL]DomRGH3ROtPHURV 
,VWRpORJ>@ ORJ.DORJ0TXHSRGHVHUUHSUHVHQWDGRJUDILFDPHQWHSHOD
UHWDLOXVWUDGDQD)LJXUD

)LJXUD5HSUHVHQWDomRJUiILFDGDGHSHQGrQFLDGDYLVFRVLGDGHLQWUtQVHFDFRPRSHVRPROHFXODU

6.5 Determinao das dimenses moleculares de um polmero em


soluo
&RPRGLVFXWLGRDQWHULRUPHQWHDYLVFRVLGDGHGHVROXo}HVGHSROtPHURVpIXQomRGDV
SURSULHGDGHVKLGURGLQkPLFDVRXVHMDSURSULHGDGHVUHODFLRQDGDVDRPRYLPHQWRGH
XPDPDFURPROpFXODHPVROXomR
$ YLVFRVLGDGH p SURSRUFLRQDO DR YROXPH HIHWLYR GD PDFURPROpFXOD HP VROXomR
LVWR p GR VHX YROXPH KLGURGLQkPLFR HIHWLYR 4XDQWR PDLRU IRU R YROXPH
KLGURGLQkPLFRPDLRUVHUiDYLVFRVLGDGH
$VPHGLGDVGHYLVFRVLGDGHIRUQHFHPHQWmRGDGRVVREUHRYROXPHPROHFXODUTXH
RSROtPHURDVVXPHHPVROXomR4XDQGRDYLVFRVLGDGHpGHWHUPLQDGDHPFRQGLo}HV
WHWD VROYHQWHHWHPSHUDWXUD RIDWRUGHH[SDQVmRGRQRYHORGD(TXDomR
pLJXDODXPHDHTXDomRGDYLVFRVLGDGHSRGHVHUGHVFULWDFRPR

[] = K . M
1
2 (6.25)

VHQGRDFRQVWDQWH.GHILQLGDSHODVHJXLQWHHTXDomR
3
r02
2

K = (6.26)

M

 9LVFRVLPHWULD
RQGH r02 pDGLVWkQFLDHVWUHPRDH[WUHPRTXDGUiWLFDPpGLDGDFDGHLDSROLPpULFD
PHGLGD VRE FRQGLo}HV WHWD H  p D FRQVWDQWH XQLYHUVDO GH )ORU\ SDUD FDGHLDV
SROLPpULFDV OLQHDUHV H IOH[tYHLV  WDPEpP SDUD FRQGLo}HV WHWD $ FRQVWDQWH GH )ORU\
SRVVXLRYDORUGH[G/J
&RPELQDQGR DV (TXDo}HV  H  D YLVFRVLGDGH LQWUtQVHFD SRGH VHU
UHODFLRQDGD j GLVWkQFLD H[WUHPRDH[WUHPR TXDGUiWLFD PpGLD VHJXQGR D (TXDomR

3
r02 2
= (6.27)

M
$ (TXDomR  GHVFUHYH D YLVFRVLGDGH LQWUtQVHFD VRE FRQGLo}HV WHWD (OD p
SURSRUFLRQDO DR FXER GD GLPHQVmR OLQHDU GD FDGHLD HQRYHODGD DOHDWRULDPHQWH RX
VHMD GD GLVWkQFLD H[WUHPRDH[WUHPR TXDGUiWLFD PpGLD (VWD GLVWkQFLD p GHILQLGD
FRPR YROXPH KLGURGLQkPLFR 2V YDORUHV GH r02  SRGHP VHU FDOFXODGRV D SDUWLU GRV
YDORUHV GH s02 VHJXQGR D (TXDomR  YHU FDStWXOR   3RU RXWUR ODGR R UDLR GH
JLUDomR TXDGUiWLFR PpGLR SRGH VHU GHWHUPLQDGR H[SHULPHQWDOPHQWH D SDUWLU GH
PHGLGDVGHHVSDOKDPHQWRGHOX]FRPRGHVFULWRQRFDStWXOR

6.6 Efeito do solvente na viscosidade de solues diludas de


polmeros
7DQWRDYLVFRVLGDGHLQWUtQVHFDFRPRRFRHILFLHQWHDQJXODUGDFXUYDGHVSFYHUVXVF
)LJXUD   GHSHQGHP GD QDWXUH]D GR VROYHQWH ,VWR RFRUUH SRUTXH R QRYHOR
SROLPpULFR VRIUH H[SDQVmR PDLRU RX PHQRU GHSHQGHQGR GDV LQWHUDo}HV SROtPHUR
VROYHQWH 4XDQWR PDLRU IRU D DILQLGDGH HQWUH SROtPHUR H VROYHQWH PDLRU VHUi R
YROXPHHIHWLYRGRQRYHORSROLPpULFRHPVROXomRHPDLRUVHUiDYLVFRVLGDGH
SERPVROYHQWHFDGHLDVH[SDQGLGDV
SPDXVROYHQWHFDGHLDVHQFROKLGDV
SVROYHQWH LGHDO RX VROYHQWH WHWD  GLPHQV}HV QmR SHUWXUEDGDV R YROXPH GD
PDFURPROpFXOD p HVWLPDGR SHOD GLVWkQFLD H[WUHPRDH[WUHPR TXDGUiWLFD PpGLD
GHWHUPLQDGDVREFRQGLo}HVWHWD

&DUDFWHUL]DomRGH3ROtPHURV 
$)LJXUDUHSUHVHQWDXPQRYHORSROLPpULFRTXDQGRH[SDQGLGRHHQFROKLGR6H
RVROYHQWHLQWHUDJHSRXFRFRPDPDFURPROpFXOD PDXVROYHQWH RFRQWDWRSROtPHUR
SROtPHURpPDLVSURYiYHOID]HQGRFRPTXHRQRYHORVHHQFROKD )LJXUDD 6HR
VROYHQWH LQWHUDJH EHP FRP D PDFURPROpFXOD ERP VROYHQWH  R FRQWDWR SROtPHUR
VROYHQWHpPDLVSURYiYHOGRTXHRFRQWDWRSROtPHURSROtPHURHRQRYHORVHH[SDQGH
)LJXUD E  $ FDGHLD HQFROKLGD RIHUHFH PHQRV UHVLVWrQFLD KLGURGLQkPLFD
UHVLVWrQFLD DR IOX[R HSRUWDQWRVXDVROXomRDSUHVHQWDPHQRUYLVFRVLGDGHGRTXH
XPDVROXomRFRQWHQGRXPDFDGHLDHVWHQGLGDGHPHVPRSHVRPROHFXODU

)LJXUD(VTXHPDGDFRQIRUPDomRGHXPQRYHORSROLPpULFRHPIXQomRGDDILQLGDGHFRPRVROYHQWH
 D HQFROKLGD E H[SDQGLGD

1R WySLFR DQWHULRU IRUDP GLVFXWLGDV DV GLPHQV}HV GH XPD PDFURPROpFXOD VRE
FRQGLo}HVWHWD1RFDVRHPTXHDPDFURPROpFXODpGLVVROYLGDHPXPERPVROYHQWH
DYLVFRVLGDGHLQWUtQVHFDpGHILQLGDFRPR
3
2 2
r
[] = M
(6.28)

RQGH r  p D GLVWkQFLD TXDGUiWLFD PpGLD GR QRYHOR HP XP VROYHQWH TXDOTXHU
2

GLIHUHQWHGRVROYHQWHWHWD(PXPVROYHQWHQmRLGHDORIDWRUGHH[SDQVmRGHYHVHU
FRQVLGHUDGR YHUFDStWXOR RXVHMD
1 1
r 2 2
= r02 2
(6.29)

 9LVFRVLPHWULD
r02
&RQVLGHUDQGRD(TXDomRHDVVXPLQGRTXHDUD]mR M pXPDIXQomRGD
HVWUXWXUD GD FDGHLD H LQGHSHQGH GR PHLR RX GR SHVR PROHFXODU D YLVFRVLGDGH
LQWUtQVHFDHPXPVROYHQWHTXDOTXHUSRGHVHUGHILQLGDFRPR
3
r02 2 1
= M 2 3 = K .M 12 3

(6.30)

M

$QDOLVDQGR DV HTXDo}HV GHVFULWDV DFLPD FRQFOXLVH TXH R YROXPH GD
PDFURPROpFXOD HP VROXomR SRGH VHU FDOFXODGR D SDUWLU GH PHGLGDV GH YLVFRVLGDGH
LQWUtQVHFD
8PD YH] TXH R QRYHOR LQFKD GH PRGR GLIHUHQWH GH DFRUGR FRP R VROYHQWH p
LQWHUHVVDQWHUHODFLRQDUDYLVFRVLGDGHLQWUtQVHFDFRPRVSDUkPHWURVWHUPRGLQkPLFRV
GHDILQLGDGHHQWUHSROtPHURHVROYHQWH9iULRVHVWXGRVWrPVLGRGHVHQYROYLGRVSDUD
HVWH ILP 3DUD SROtPHURV IOH[tYHLV IRL SRVVtYHO UHODFLRQDU D YLVFRVLGDGH FRP R
VHJXQGRFRHILFLHQWHYLULDO1RFDVRGHSROtPHURVFRPFDGHLDVUtJLGDVQmRH[LVWHHVWD
FRUUHODomR$OJXPDVUHODo}HVIRUDPSURSRVWDVWDLVFRPRDVGHVFULWDVDVHJXLU
S(TXDomRGH.ULJEDXPUHODFLRQDRVHJXQGRFRHILFLHQWHYLULDOREWLGRSRUSUHVVmR
RVPyWLFD$HDYLVFRVLGDGHLQWUtQVHFD
[] = [] + 0,50.A2M (6.31)
>@pDYLVFRVLGDGHLQWUtQVHFDPHGLGDHPVROYHQWHWHWD

S(TXDomRGH6WRFNPD\HUH)L[PDQUHODFLRQDDYLVFRVLGDGHLQWUtQVHFDFRPXPD
TXDQWLGDGH%TXHpIXQomRGRSDUkPHWURGHLQWHUDomR.
[] = K.M + 0,51B.M (6.32)
RQGH.pDFRQVWDQWHGHWHUPLQDGDHPFRQGLo}HVWHWD0pRSHVRPROHFXODUpD
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2
v sp (1 2 )
B= (6.33)
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Q~PHURGH$YRJDGUR

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6.7 Efeito do peso molecular na viscosidade
$ YLVFRVLGDGH GH VROXo}HV GLOXtGDV p EDVWDQWH DIHWDGD SHOR SHVR PROHFXODU 2
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GLIHUHQWHVSHVRVPROHFXODUHV 0!0!0!0 

6.8 Viscosidade em solues de polieletrlitos


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GDPDFURPROpFXODQDYLVFRVLGDGHGDVVROXo}HVGLOXtGDV$PROpFXODGHVWHVSROtPHURV
VRIUHYDULDo}HVFRQVLGHUiYHLVQRVHXYROXPHKLGURGLQkPLFRGHSHQGHQGRGRJUDXGH
GLVVRFLDomR7RPHPRVFRPRH[HPSORRSROL iFLGRDFUtOLFR RXSROL iFLGRPHWDFUtOL
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D HVWDV VROXo}HV R SROLiFLGR UHDJH IRUPDQGR VDLV GH VyGLR RX SRWiVVLR (VWHV VDLV

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o}HVVmRPDLRUHVFRPRDXPHQWRGDFRQFHQWUDomRGDVROXomRHSRUWDQWRRHIHLWRQD
YLVFRVLGDGHpDLQGDPDLRU
$ YLVFRVLGDGH GD VROXomR GH SROLiFLGR DXPHQWD FRP R DXPHQWR GR S+ DWp XP
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WLSR D 8&67H E /&67

6.10 Tamanho molecular de polmeros ramificados


$YLVFRVLGDGHLQWUtQVHFDGHXPSROtPHURHPVROXomRpXPSDUkPHWURTXHGHSHQGH
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(6.35)

M
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PHVPRSHVRPROHFXODUHFRPQ~PHURGHUDPLILFDo}HVGLIHUHQWH


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PRGHORVTXHUHODFLRQDPRSDUkPHWUR g FRPRQ~PHURGHUDPLILFDo}HVIGHXP
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Modelo de Stockmayer e Fixman


3
2 2 2 ( f 1)
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g = f f +2

(6.36)

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Modelo de Zimm e Kilb


3 [0,39( f 1)+ 0,196]
2 2
g =
f
(6.37)
0,586
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7.1 Introduo
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VXEVWkQFLDVVHPRYHUmRFRPPDLRURXPHQRUUDSLGH]GHSHQGHQGRGDVXDDILQLGDGH
FRPDIDVHHVWDFLRQiULDHFRPDIDVHPyYHO
$ FURPDWRJUDILD SRGH VHU VXEGLYLGLGD HP GLIHUHQWHV JUXSRV $ VHJXLU VHUmR
OLVWDGRVDOJXQVH[HPSORVGHVXEGLYLVmR

Subdiviso baseada na geometria do leito cromatogrfico


S &URPDWRJUDILD HP FROXQD  XPD FROXQD XVXDOPHQWH GH YLGUR RX GH DoR
LQR[LGiYHO p HPSDFRWDGD FRP R PDWHULDO DWLYR IDVH HVWDFLRQiULD  DWUDYpV GR
TXDODPLVWXUDDVHUVHSDUDGDIOXL
S &URPDWRJUDILD SODQDU  HVWH WLSR GH FURPDWRJUDILD LQFOXL D FURPDWRJUDILD HP
FDPDGDILQDHDFURPDWRJUDILDHPSDSHO

Subdiviso baseada no estado de agregao da fase mvel


S &URPDWRJUDILD JDVRVD RX FURPDWRJUDILD D JiV *&   D IDVH PyYHO p XP JiV
FDUUHDGRU$FURPDWRJUDILDJDVRVDpXPDWpFQLFDGHFURPDWRJUDILDHPFROXQDHD
IDVHHVWDFLRQiULDSRGHVHUXPOtTXLGRRXXPVyOLGR
S &URPDWRJUDILDOtTXLGDRXFURPDWRJUDILDDOtTXLGR /& DIDVHPyYHOpXPOtTXLGR
$FURPDWRJUDILDOtTXLGDSRGHVHUHPFROXQDRXSODQDU

Subdiviso baseada no mecanismo de separao


S &URPDWRJUDILD GH SDUWLomR  HVWD FURPDWRJUDILD UHTXHU XPD IDVH HVWDFLRQiULD QD
TXDORVFRPSRQHQWHVGDDPRVWUDSRVVXHPGLIHUHQWHVVROXELOLGDGHV

&DUDFWHUL]DomRGH3ROtPHURV 
S &URPDWRJUDILD GH H[FOXVmR SRU WDPDQKR  D IDVH HVWDFLRQiULD FRQWpP SRURV GH
WDPDQKRV YDULDGRV H D VHSDUDomR DFRQWHFH D SDUWLU GH WDPDQKRV GLIHUHQWHV GD
PROpFXOD HP UHODomR DR WDPDQKR GRV SRURV GD IDVH HVWDFLRQiULD (VWH WLSR GH
FURPDWRJUDILDpJHUDOPHQWHXVDGRSDUDVHSDUDomRGHPDFURPROpFXODV
S &URPDWRJUDILDSRUDGVRUomRDIDVHHVWDFLRQiULDSRVVXLFHQWURVDWLYRVFDSD]HVGH
DGVRUYHUHP RV FRPSRQHQWHV GD PLVWXUD D VHU DQDOLVDGD $ DGVRUomR p
LQIOXHQFLDGDEDVLFDPHQWHSHODVIRUoDVLQWHUPROHFXODUHVSRODUHV
$)LJXUDLOXVWUDRVGLYHUVRVWLSRVWpFQLFDVFURPDWRJUiILFDV

7.2 Teoria das colunas


7DQWR QD FURPDWRJUDILD JDVRVD FRPR QD FURPDWRJUDILD OtTXLGD SRU HOXLomR D IDVH
HVWDFLRQiULD UHVSRQViYHO SHOD VHSDUDomR p FRORFDGD GHQWUR GH XPD FROXQD TXH
SRGHVHUGHYLGURRXGHDoRLQR[LGiYHO1DFURPDWRJUDILDOtTXLGDGHDOWDUHVROXomR
+3/& DFROXQDpVHPSUHGHDoRLQR[LGiYHO
2 VXFHVVR GH XPD VHSDUDomR FURPDWRJUiILFD GHSHQGH IXQGDPHQWDOPHQWH GD
TXDOLGDGHGDIDVHHVWDFLRQiULDRXVHMDGRUHFKHLRGDVFROXQDV$VHSDUDomRHQYROYH
DOJXQV UHTXLVLWRV EiVLFRV WDLV FRPR D UHVROXomR D VHOHWLYLGDGH GD FROXQD D
YHORFLGDGHGRIOX[RGDIDVHPyYHOHDFDSDFLGDGHGHVHSDUDomRGDFROXQD
e LPSRUWDQWH HQWmR DQWHV GH GHVFUHYHU DV GLYHUVDV WpFQLFDV FURPDWRJUiILFDV
GLVFXWLU RV SDUkPHWURV TXH HQYROYHP XPD ERD VHSDUDomR FURPDWRJUiILFD $OJXPDV
GHILQLo}HVVmROLVWDGDVDVHJXLU
S 7HPSR GH UHWHQomR  p R WHPSR TXH D VXEVWkQFLD OHYD SDUD SHUFRUUHU D FROXQD
GHVGHDVXDLQMHomRDWpDVXDSDVVDJHPSHORGHWHFWRU1DFURPDWRJUDILDOtTXLGD
HVWHWHPSRpWDPEpPFRQKHFLGRFRPRWHPSRGHHOXLomR
S 9ROXPH GH UHWHQomR  p R YROXPH GD IDVH PyYHO TXH HOXL GHVGH D LQMHomR GD
DPRVWUDDWpDSDVVDJHPGDDPRVWUDSHORGHWHFWRU1DFURPDWRJUDILDOtTXLGDHVWH
YROXPH WDPEpP p FRQKHFLGR FRPR YROXPH GH HOXLomR 2 WHPSR H R YROXPH GH
UHWHQomRSRVVXHPRPHVPRVLJQLILFDGRHVmRXWLOL]DGRVSHORVDXWRUHVLQGLVFULPL
QDGDPHQWH

 &URPDWRJUDILD
)LJXUD$VUDPLILFDo}HVGDFURPDWRJUDILD

7.2.1 Eficincia da coluna


$ HILFLrQFLD GD FROXQD p PHGLGD HP WHUPRV GH Q~PHUR GH SUDWRV WHyULFRV 1 GH
DFRUGRFRPD(TXDomR
2
2 t
t
N = 16 R ou N = 5,5 R (7.1)
w w1
2
RQGH1pRQ~PHURGHSUDWRVWHyULFRVW5pRWHPSRGHUHWHQomRUHODWLYRDRPi[LPR
GRSLFRHZpDODUJXUDGRSLFRPHGLGRQDOLQKDEDVH$PHLDODUJXUDZpDODUJXUD
GR SLFR FRUUHVSRQGHQWH j VXD PHLD DOWXUD $ )LJXUD  LOXVWUD R PpWRGR SDUD D
GHWHUPLQDomRGRQ~PHURGHSUDWRVWHyULFRV

&DUDFWHUL]DomRGH3ROtPHURV 
)LJXUD&iOFXORGRQ~PHURGHSUDWRVWHyULFRV

$ (TXDomR  FRPSDUD D ODUJXUD GR SLFR FRP R WHPSR HP TXH R FRPSRQHQWH
ILFRXUHWLGRQDFROXQD2Q~PHURGHSUDWRVWHyULFRVpSURSRUFLRQDODRFRPSULPHQWR
GD FROXQD *HUDOPHQWH FROXQDV PDLV FRPSULGDV SRVVXHP XP Q~PHUR GH SUDWRV
WHyULFRVPDLRUSRUpPRFDVLRQDPXPDXPHQWRQDSUHVVmRGRVLVWHPD&RQVLGHUDQGR
TXH DV FROXQDV VmR FRPHUFLDOL]DGDV HP YiULRV WDPDQKRV p LPSRUWDQWH DYDOLDU D
HILFLrQFLD GD FROXQD GH XPD IRUPD LQGHSHQGHQWH GR Q~PHUR GH SUDWRV WHyULFRV
'HVWH PRGR p PHOKRU XWLOL]DU R WHUPR DOWXUD HTXLYDOHQWH D XP SUDWR WHyULFR
+(73 TXHpUHODFLRQDGDDRQ~PHURGHSUDWRVWHyULFRVVHJXQGRD(TXDomR
L
HETP = (7.2)
N
RQGH/pRFRPSULPHQWRGDFROXQDJHUDOPHQWHHPPLOtPHWURVH1pRQ~PHURGH
SUDWRVWHyULFRV4XDQWRPHOKRUIRUDHILFLrQFLDGDFROXQDPHQRUHVVHUmRRVYDORUHV
GH+(736HFRPSDUDUPRVFROXQDVGHPHVPRFRPSULPHQWR/DHILFLrQFLDVHUiWDQWR
PDLRUTXDQWRPDLRUIRURQ~PHURGHSUDWRVWHyULFRV1
$ DOWXUD HTXLYDOHQWH D XP SUDWR WHyULFR GHSHQGH GD YHORFLGDGH GH IOX[R GD IDVH
PyYHO (VWD GHSHQGrQFLD p LOXVWUDGD QD )LJXUD  RQGH D +(73 p FRORFDGD HP
IXQomR GD YHORFLGDGH GH IOX[R (VWD GHSHQGrQFLD p FRQKHFLGD FRPR UHSUHVHQWDomR
JUiILFD GH YDQ 'HHPWHU &RPR LQGLFDGR QD )LJXUD  SDUD XPD ERD HILFLrQFLD D
YHORFLGDGHGRIOX[RXWLOL]DGRQRVH[SHULPHQWRVQmRSRGHVHUPXLWREDL[DQHPPXLWR
DOWD $ FXUYD DSUHVHQWDGD QD ILJXUD p R UHVXOWDGR GD FRPSRVLomR GH YiULRV IDWRUHV
TXHLQIOXHQFLDPDDOWXUDGRSUDWRWDLVFRPRSURFHVVRGHGLIXVmRLUUHJXODULGDGHGH
IOX[RHWF

 &URPDWRJUDILD


)LJXUD'HSHQGrQFLDGD+(73FRPDYHORFLGDGHGHIOX[RGDIDVHPyYHO 'LDJUDPDGHYDQ 'HHPWHU  D 


HIHLWRGDGLIXVmRPROHFXODU E HIHLWRGDUHVLVWrQFLDjWUDQVIHUrQFLDGHPDVVD 

7.2.2 Seletividade da coluna


$ VHOHWLYLGDGH GH XPD FROXQD  p GHILQLGD SHOD VHSDUDomR UHODWLYD GRV SLFRV H p
GDGDSHOD(TXDomR
t R2 t m K 2
= = (7.3)
t R1 t m K1
RQGHW5HW5VmRRVWHPSRVGHUHWHQomRGRVFRPSRQHQWHVHUHVSHFWLYDPHQWHH
WP p R WHPSR GH UHWHQomR GR FRPSRQHQWH QmR UHWLGR QD FROXQD 1D FURPDWRJUDILD
JDVRVDHQDFURPDWRJUDILDOtTXLGDSRUDGVRUomRHVWHWHPSRFRUUHVSRQGHDRWHPSR
GHUHWHQomRGRVROYHQWH.H.FRUUHVSRQGHPDRVFRHILFLHQWHVGHGLVWULEXLomRGRV
FRPSRQHQWHVHUHVSHFWLYDPHQWH
2FRHILFLHQWHGHGLVWULEXLomRpGHILQLGRSHODUD]mRHQWUHDFRQFHQWUDomRGHVROXWR
QDIDVHHVWDFLRQiULDHDFRQFHQWUDomRGHVROXWRQDIDVHPyYHO
1D FURPDWRJUDILD OtTXLGD R FRHILFLHQWH GH GLVWULEXLomR p IUHTHQWHPHQWH
GHILQLGRGHDFRUGRFRPRPHFDQLVPRGHVHSDUDomRFRPR
S FRHILFLHQWHGHSDUWLomRQDFURPDWRJUDILDOtTXLGDGHSDUWLomR
S FRHILFLHQWHGHSHUPHDomRQDFURPDWRJUDILDGHH[FOXVmRSRUWDPDQKR
S FRHILFLHQWHGHDGVRUomRQDFURPDWRJUDILDOtTXLGDGHDGVRUomR

&DUDFWHUL]DomRGH3ROtPHURV 
S FRHILFLHQWHGHGLVWULEXLomRQDFURPDWRJUDILDGHWURFDL{QLFD
2YROXPHGHUHWHQomRGHXPSLFRHPXPDFURPDWRJUDILDOtTXLGDpGHILQLGRFRPR

V R = Vm + KVest (7.4)

RQGH
9P YROXPHGDIDVHPyYHOQRVLQWHUVWtFLRVGRUHFKHLRGDFROXQDRXVHMDRYROXPH
PRUWR
9HVW YROXPHGDIDVHHVWDFLRQiULD QDFURPDWRJUDILDGHSDUWLomR RX
 YROXPHGHSRURV QDFURPDWRJUDILDGHH[FOXVmRSRUWDPDQKR RX
 iUHDVXSHUILFLDO QDFURPDWRJUDILDSRUDGVRUomR RX
 FDSDFLGDGHGHWURFDL{QLFD QDFURPDWRJUDILDGHWURFDL{QLFD 

'H DFRUGR FRP D (TXDomR  TXDQWR PDLRU IRU R YDORU GH . PDLRU VHUi D
DILQLGDGH GR VROXWR SHOD IDVH HVWDFLRQiULD H SRUWDQWR PDLRU VHUi D UHWHQomR GHVWH
VROXWR
$ VHOHWLYLGDGH GD FROXQD SRGH VHU PHOKRUDGD PXGDQGRVH R FRHILFLHQWH GH
GLVWULEXLomR (VWH FRHILFLHQWH SRGH VHU DOWHUDGR PXGDQGRVH D IDVH PyYHO D IDVH
HVWDFLRQiULDRXDQDWXUH]DGRVROXWR

7.2.3 Resoluo
2 REMHWLYR GD FURPDWRJUDILD p VHSDUDU RV FRPSRQHQWHV GH XPD PLVWXUD HP XP
WHPSRUD]RiYHO$UHVROXomR5HQWUHGRLVSLFRVSRGHVHUTXDQWLWDWLYDPHQWHPHGLGD
DSDUWLUGD(TXDomR

t R 2 t R1 2t
R= =
w2 + w1 w2 + w1 (7.5)

2
RQGH W5 H W5 FRUUHVSRQGHP DRV WHPSRV GH UHWHQomR GRV FRPSRQHQWHV PHGLGRV QR
Pi[LPR GRV SLFRV H W p D GLIHUHQoD HQWUH  W5 H W5 2V YDORUHV GH Z H Z
FRUUHVSRQGHP jV ODUJXUDV GRV SLFRV HP XQLGDGHV GH WHPSR $ )LJXUD  LOXVWUD D
GHILQLomRGHUHVROXomR

 &URPDWRJUDILD


)LJXUD,OXVWUDomRGDGHWHUPLQDomRGDUHVROXomRGRFURPDWRJUDPD

$UHVROXomRGHSHQGHGDODUJXUDGRVSLFRVHGDGLVWkQFLDHQWUHRVSLFRV$)LJXUD
 LOXVWUD D UHVROXomR GH XP FURPDWRJUDPD FRQWHQGR GRLV SLFRV HP IXQomR GD
VHOHWLYLGDGHRXGDHILFLrQFLD1RFURPDWRJUDPDDSUHVHQWDGDQD)LJXUDDREVHUYD
VHXPDEDL[DUHVROXomRGRVSLFRV$UHVROXomRSRGHVHUPHOKRUDGDDXPHQWDQGRVHD
HILFLrQFLD )LJXUD E  RX D VHOHWLYLGDGH GD FROXQD )LJXUD F  2 DXPHQWR GD
HILFLrQFLD UHVXOWD HP XPD GLPLQXLomR GD ODUJXUD GD EDQGD $ VHSDUDomR p PDLV
HILFLHQWH PDQWHQGRVH D GLVWkQFLD HQWUH RV SLFRV LQDOWHUDGD 4XDQGR D UHVROXomR p
DXPHQWDGDGHYLGRDRDXPHQWRQDVHOHWLYLGDGHGDFROXQD )LJXUDF DGLVWkQFLD
HQWUHRVSLFRVpDOWHUDGD1HVWHFDVRRDXPHQWRGDUHVROXomRHQYROYHXPDXPHQWR
QRWHPSRGHDQiOLVHYLVWRTXHDVHOHWLYLGDGHpJRYHUQDGDSHODVLQWHUDo}HVGRVROXWR
FRP R VROYHQWH H FRP D IDVH HVWDFLRQiULD $XPHQWDQGRVH D TXDQWLGDGH GD IDVH
HVWDFLRQiULDDUHVROXomRDXPHQWDUiSRUpPRWHPSRGHDQiOLVHWDPEpPDXPHQWDUi

&DUDFWHUL]DomRGH3ROtPHURV 
)LJXUD5HVROXomRGHXPFURPDWRJUDPDFRPGRLVFRPSRQHQWHV D FURPDWRJUDPDFRPVXSHUSRVLomRGH
EDQGDV E FURPDWRJUDPDFRPUHVROXomRPHOKRUDGDGHYLGRDRDXPHQWRGDHILFLrQFLDGDFR OXQD F 
FURPDWRJUDPDFRPUHVROXomRPHOKRUDGDGHYLGRDRDXPHQWRGDVHOHWLYLGDGH 

7.3 Cromatografia gasosa


$FURPDWRJUDILDJDVRVDpXPDWpFQLFDGHVHSDUDomRHPTXHVXEVWkQFLDVFDSD]HVGH
VHYRODWLOL]DUHPSHUFRODPHPXPDFRUUHQWHGHJiVDWUDYpVGDIDVHHVWDFLRQiULD
'HSHQGHQGR GD QDWXUH]D GD IDVH HVWDFLRQiULD D FURPDWRJUDILD JDVRVD SRGH VHU
VXEGLYLGLGDHPGRLVJUXSRVFURPDWRJUDILDJiVOtTXLGR */& HFURPDWRJUDILDJiV
VyOLGR *6& 

7.3.1 Cromatografia gs lquido (GLC)


7.3.1.1 Princpio da tcnica
1D FURPDWRJUDILD JiV  OtTXLGR RV FRPSRQHQWHV D VHUHP VHSDUDGRV VmR FDUUHDGRV
DWUDYpV GD FROXQD SRU XP JiV LQHUWH FKDPDGR JiV FDUUHDGRU $ IDVH HVWDFLRQiULD
FRQVLVWHHPXPILOPHILQRRXXPOtTXLGRQmRYROiWLODGHULGRDXPVyOLGRLQHUWH$
PLVWXUDTXHFRQVWLWXLDDPRVWUDVRIUHXPDSDUWLomRHQWUHRJiVFDUUHDGRUHROtTXLGR
QmRYROiWLO IDVH HVWDFLRQiULD  TXH HVWi VXSRUWDGR HP XP VyOLGR LQHUWH VXSRUWH
VyOLGR 

 &URPDWRJUDILD
2OtTXLGRTXHFRQVWLWXLDIDVHHVWDFLRQiULDUHWDUGDVHOHWLYDPHQWHDHOXLomRGRV
FRPSRQHQWHV GD PLVWXUD GH DFRUGR FRP R VHX FRHILFLHQWH GH GLVWULEXLomR HQWUH D
IDVHOtTXLGDHDIDVHYDSRU2VFRPSRQHQWHVGDPLVWXUDVLWXDGRVQDFRUUHQWHJDVRVD
GHL[DPHQWmRDFROXQDHVmRGHWHFWDGRVHPIXQomRGRWHPSRDSyVDVXDSDVVDJHP
SRU XP GHWHFWRU DSURSULDGR 4XDQWR PDLV WHPSR D VXEVWkQFLD SHUPDQHFHU QD IDVH
PyYHOPDLVUiSLGRVHUiRVHXDUUDVWHSHODFRUUHQWHGHYDSRU
2 SURFHVVR GH VHSDUDomR FRQVLVWH QD FDSDFLGDGH GH GLIHUHQWHV VXEVWkQFLDV
GLVWULEXtUHPVH HQWUH D IDVH OtTXLGD H D IDVH YDSRU $ VHSDUDomR GDV VXEVWkQFLDV
GHSHQGHGDYRODWLOLGDGHUHODWLYDGHFDGDFRPSRQHQWHGDPLVWXUD(VWDYRODWLOLGDGHp
IXQomRGDSUHVVmRGHYDSRUGRFRPSRQHQWHQRVLVWHPD$SUHVVmRGHYDSRUGHFDGD
FRPSRQHQWH p SRU VXD YH] IXQomR GDV IRUoDV GH LQWHUDomR HQWUH R VROXWR H D IDVH
OtTXLGDHVWDFLRQiULD4XDQGRH[LVWHXPDERDLQWHUDomRVROYHQWHVROXWRDSUHVVmR
GHYDSRUpPHQRUUHVXOWDQGRHPXPWHPSRPDLRUGHUHWHQomRGRVROXWRQDFROXQD

7.3.1.2 Descrio do cromatgrafo


$ )LJXUD  DSUHVHQWD R HVTXHPD GH XP FURPDWyJUDIR JDVRVR FXMDV SDUWHV
FRQVWLWXLQWHVVmRGHVFULWDVDVHJXLU

)LJXUD'LDJUDPDHVTXHPiWLFRGHXPFURPDWyJUDIRJDVRVR

 8PFLOLQGURFRQWHQGRRJiVFDUUHDGRU KLGURJrQLRKpOLRDUJ{QLRRXQLWURJrQLR FRP


IOX[RFRQWURODGRHUHJXODGRUGHSUHVVmRDSUHVHQoDGHR[LJrQLRRXiJXDQRJiV
FDUUHDGRU p SUHMXGLFLDO SDUD D IDVH OtTXLGD HVWDFLRQiULD 3RUWDQWR GHYHP VHU

&DUDFWHUL]DomRGH3ROtPHURV 
XWLOL]DGRVJDVHVHVSHFLDLVFRPDOWDSXUH]D2IOX[RGHJiVQDFROXQDpDMXVWDGR
SRU PLFURYiOYXODV 2 JiV SDVVD SHOR LQMHWRU RQGH D DPRVWUD D VHU DQDOLVDGD p
LQMHWDGDHHPVHJXLGDDWUDYHVVDDFROXQDHRGHWHFWRU
 6LVWHPD GH LQMHomR GH DPRVWUD  VXEVWkQFLDV OtTXLGDV VmR LQWURGX]LGDV FRP
VHULQJDV6XEVWkQFLDVVyOLGDVVmRLQMHWDGDVHPVROXomRXWLOL]DQGRVHXPVROYHQWH
TXH QmR LQWHUILUD QRV FRPSRQHQWHV TXH HVWmR VHQGR DQDOLVDGRV *HUDOPHQWH R
VROYHQWH SRVVXL XP WHPSR GH UHWHQomR PXLWR EDL[R H SRUWDQWR p R SULPHLUR D
VHU HOXtGR $V DPRVWUDV VmR LQMHWDGDV DWUDYpV GH XP VHSWR GH ERUUDFKD
XWLOL]DQGRVHPLFURVHULQJDV
 $FROXQDDVFROXQDVVmRIHLWDVGHFREUHDoRDOXPtQLRRXYLGUR4XDQWRPDLRU
IRU R FRPSULPHQWR GD FROXQD PDLRU VHUi D UHVROXomR 3RU RXWUR ODGR HODV
UHTXHUHPXPDSUHVVmRGHHQWUDGDPDLRU7DLVFROXQDVVmRHPSDFRWDGDVFRPXP
VXSRUWHVyOLGRDILPGHSURPRYHUXPDiUHDVXSHUILFLDOXQLIRUPHHLQHUWHVREUHD
TXDO D IDVH OtTXLGD HVWDFLRQiULD LUi VH GLVWULEXLU$ TXDQWLGDGH GH IDVH OtTXLGD
XVDGD FRPR IDVH HVWDFLRQiULD GHYH VHU VXILFLHQWH SDUD FREULU DV SDUWtFXODV GR
VXSRUWHVyOLGRFRPXPDFDPDGDILQDHXQLIRUPH
 'HWHFWRUHV  RV GHWHFWRUHV LQGLFDP D SUHVHQoD H D TXDQWLGDGH GRV FRPSRQHQWHV
QRHOXHQWHGHXPDFROXQDFURPDWRJUiILFD([LVWHPGRLVWLSRVGHGHWHFWRUHVPDLV
SRSXODUHVRGHFRQGXWLYLGDGHWpUPLFDHRGHLRQL]DomRGHFKDPD
S &RQGXWLYLGDGH WpUPLFD  HPSUHJD XP ILODPHQWR GH WXQJVWrQLR DTXHFLGR 4XDQGR
DV PROpFXODV PLVWXUDGDV DR JiV FDUUHDGRU SDVVDP DWUDYpV GHVWH ILODPHQWR
DTXHFLGR R ILODPHQWR SHUGH FDORU R TXDO p WUDQVIHULGR SRU FRQGXWLYLGDGH
WpUPLFD $V PROpFXODV GR JiV HQFRQWUDP R ILODPHQWR DTXHFLGR H VRIUHP XP
DXPHQWR GD VXD HQHUJLD FLQpWLFD 4XDQWR PDLRU IRU R Q~PHUR GH FROLV}HV
PROHFXODUHV FRP R ILODPHQWR PDLRU VHUi D SHUGD GH FDORU GR ILODPHQWR
0ROpFXODVPHQRUHVSRVVXHPPDLRUPRELOLGDGHHUHVXOWDPHPXPQ~PHURPDLRU
GHFROLV}HVHSRUWDQWRPDLRUFRQGXWLYLGDGHWpUPLFD3DUDHVWHWLSRGHGHWHFWRU
UHFRPHQGDVH KLGURJrQLR KpOLR RX DUJ{QLR FRPR JiV FDUUHDGRU SRUTXH HVWHV
SRVVXHP PHQRU SHVR PROHFXODU H SRUWDQWR PDLRU FRQGXWLYLGDGH WpUPLFD $V
VXEVWkQFLDVDVHUHPDQDOLVDGDVSRVVXHPVHPSUHSHVRPROHFXODUPDLRUGRTXHR
JiV FDUUHDGRU 4XDQGR HODV SDVVDP SHOR GHWHFWRU D FRQGXWLYLGDGH WpUPLFD p
UHGX]LGDHDGLIHUHQoDpUHJLVWUDGD
S ,RQL]DomRGHFKDPD ),' RJiVHOXHQWHpPLVWXUDGRFRPKLGURJrQLRHTXHLPDGR
HP DWPRVIHUD GH DU RX R[LJrQLR 2V tRQV H HOpWURQV IRUPDGRV QD FRPEXVWmR
SDVVDP SRU HOHWURGRV GLPLQXLQGR D UHVLVWrQFLD HOpWULFD (VWH GHWHFWRU p
UHFRPHQGDGRSDUDVROXo}HVDTXRVDVSRUTXHDiJXDQmRpGHWHFWDGD

 5HJLVWUDGRU  2 UHJLVWUDGRU UHFHEH R VLQDO GR GHWHFWRU H IRUQHFH XP
FURPDWRJUDPD IRUPDGR SRU SLFRV D GLIHUHQWHV WHPSRV GH UHWHQomR $ iUHD GH

 &URPDWRJUDILD
FDGD SLFR p SURSRUFLRQDO j VXD FRQFHQWUDomR QD DPRVWUD (TXLSDPHQWRV PDLV
PRGHUQRVXWLOL]DPVLVWHPDGHDTXLVLomRGHGDGRVSRUFRPSXWDGRU

7.3.1.3 Fatores que afetam a separao de substncias


$ VHOHomR FRUUHWD GD IDVH HVWDFLRQiULD p EDVHDGD QD FRPSRVLomR GD DPRVWUD 3DUD
XPD VHSDUDomR HILFLHQWH D IDVH OtTXLGD GHYH SRVVXLU HVWUXWXUD VHPHOKDQWH j GRV
FRPSRQHQWHVGDPLVWXUD3RUH[HPSORPLVWXUDVHQYROYHQGRKLGURFDUERQHWRVGHYHP
VHU DQDOLVDGDV XWLOL]DQGRVH FROXQDV FXMD IDVH HVWDFLRQiULD p FRPSRVWD GH
KLGURFDUERQHWRV QmRYROiWHLV 6XEVWkQFLDV SRODUHV GHYHP VHU DQDOLVDGDV HP IDVH
OtTXLGDSRODU$OJXQVH[HPSORVVmRGLVFXWLGRVDVHJXLU

SSeparao de benzeno e ciclo-hexano


&RQVLGHUHPRV D VHSDUDomR GH XPD PLVWXUD FRQWHQGR EHQ]HQR H FLFORKH[DQR HP
XPDFROXQDFRQVWLWXtGDSRUXPyOHRPLQHUDO GHQDWXUH]DDSRODU FRPRIDVHOtTXLGD
HVWDFLRQiULD 2 FLFORKH[DQR SRVVXL XPD LQWHUDomR PDLRU FRP D IDVH HVWDFLRQiULD
GHYLGR j VXD PHQRU SRODULGDGH /RJR HOH p UHWLGR SRU PDLV WHPSR QD FROXQD 6H
XWLOL]DUPRV XPD FROXQD FRQVWLWXtGD SRU IWDODWR GH GLLVRFWLOD FRPR IDVH OtTXLGD
HVWDFLRQiULD R EHQ]HQR VRIUHUi PDLRU LQWHUDomR FRP HVWD IDVH H ILFDUi UHWLGR SRU
PDLVWHPSR

SSeparao de aminas
3DUD FRPSRVWRV SRODUHV D IDVH OtTXLGD HVWDFLRQiULD PDLV FRPXP p DTXHOD
FRQVWLWXtGDGHSROL JOLFROHWLOrQLFR  &$5%2:$; 3ROL JOLFROHWLOrQLFR XWLOL]DGRFRPR
IDVHHVWDFLRQiULDpXPSROtPHURGHEDL[RSHVRPROHFXODUFRQWHQGROLJDo}HVpWHUHP
VXDFDGHLDSULQFLSDO(VWDIDVHOtTXLGDHVWDFLRQiULDpUHODWLYDPHQWHSRODUHLQWHUDJH
EHPFRPVXEVWkQFLDVSRODUHVSULQFLSDOPHQWHDTXHODVFDSD]HVGHIRUPDUSRQWHVGH
KLGURJrQLR 4XDQGR XPD DPRVWUD FRQWHQGR GLIHUHQWHV DPLQDV p LQMHWDGD QR
FURPDWyJUDIRDVDPLQDVSULPiULDVLQWHUDJHPPDLVFRPDIDVHHVWDFLRQiULDGHYLGRj
PDLRU WHQGrQFLD j IRUPDomR GH SRQWHV GH KLGURJrQLR /RJR HODV VHUmR UHWLGDV SRU
PDLVWHPSRQROHLWRFURPDWRJUiILFR

SSeparao de lcoois
4XDQGR VH XWLOL]D FROXQD SRODU GR WLSR &$5%2:$; D VHSDUDomR GH iOFRRLV GH
GLIHUHQWHV SHVRV PROHFXODUHV RFRUUH HP IXQomR GD SRODULGDGH GR iOFRRO 4XDQWR
PDLRUIRUDFDGHLDKLGURFDUE{QLFDGRiOFRROPDLVIUDFDVVHUmRDVLQWHUDo}HVGRWLSR
SRQWHGHKLGURJrQLRFRPDIDVHHVWDFLRQiULDGHYLGRjPDLRUFRQWULEXLomRGDSDUWH
KLGURIyELFD GR iOFRRO OFRRLV PDLRUHV HOXLUmR PDLV IDFLOPHQWH GHYLGR j PHQRU
LQWHUDomRFRPDIDVHHVWDFLRQiULDSRODU

&DUDFWHUL]DomRGH3ROtPHURV 
4XDQGR D IDVH HVWDFLRQiULD p DSRODU D VHSDUDomR GH iOFRRLV GH WDPDQKRV
GLIHUHQWHV p EDVHDGD QR SHVR PROHFXODU 4XDQWR PDLRU IRU R SHVR PROHFXODU GR
iOFRRO PHQRU VHUi D SUHVVmR GH YDSRU H SRUWDQWR PDLV UHWLGR HOH ILFDUi QD IDVH
HVWDFLRQiULD
$OpPGDVGLIHUHQWHVLQWHUDo}HVHQWUHVROXWRHIDVHHVWDFLRQiULDDYLVFRVLGDGHGD
IDVHHVWDFLRQiULDDIHWDDVHSDUDomR9LVFRVLGDGHPXLWREDL[DIDFLOLWDDGLVWULEXLomRGR
FRPSRQHQWHQROtTXLGRHSRUWDQWRDXPHQWDRIDWRUGHVHSDUDomR
$WHPSHUDWXUDWDPEpPLQIOXHQFLDDVHSDUDomRGRVFRPSRQHQWHV2DXPHQWRGD
WHPSHUDWXUD GLPLQXL D YLVFRVLGDGH GD IDVH HVWDFLRQiULD DXPHQWDQGR R FRQWDWR
HQWUHHVWDHRVROXWRHIDYRUHFHQGRVXDGLVWULEXLomRQDIDVHHVWDFLRQiULD3RURXWUR
ODGRRDXPHQWRGDWHPSHUDWXUDDXPHQWDDFRQFHQWUDomRGRVROXWRQDIDVHYDSRU
,VWRID]FRPTXHDVHOHWLYLGDGHGLPLQXDHRVFRPSRQHQWHVHOXDPDRPHVPRWHPSR

7.3.2 Cromatografia gs slido (GSC)


1DFURPDWRJUDILDJiVVyOLGR *6& RVFRPSRQHQWHVJDVRVRVVmRVHSDUDGRVDSDUWLU
GH DGVRUomR VHOHWLYD QD VXSHUItFLH GH XP VyOLGR DWLYR SRU H[HPSOR VtOLFD JHO RX
SHQHLUDPROHFXODU$IDVHVyOLGDPDLVXWLOL]DGDSDUDVHSDUDomRGHJDVHVpDSHQHLUD
PROHFXODU (OD p FDSD] GH VHSDUDU RV FRPSRQHQWHV D SDUWLU GDV GLIHUHQoDV GH
WDPDQKRPROHFXODUHFRQILJXUDomRHDGVRUYHPROpFXODVFRPSURSULHGDGHVSRODUHV

7.3.3 Aplicao da cromatografia gasosa na caracterizao e anlise de


polmeros
3ROtPHURVSRVVXHPDOWRSHVRPROHFXODUHSRUWDQWRSUHVVmRGHYDSRUPXLWREDL[D
(OHVQmRSRGHPVHUDQDOLVDGRVGLUHWDPHQWHSRUFURPDWRJUDILDJDVRVD
$V SULQFLSDLV DSOLFDo}HV GD FURPDWRJUDILD JDVRVD QD iUHD GH SROtPHURV HVWmR
GHVFULWDVDVHJXLU
 'HWHUPLQDomRGDSXUH]DGRVPRQ{PHURVVROYHQWHVHDGLWLYRV
 $QiOLVHGRVFRPSRQHQWHVYROiWHLVQRVSROtPHURVWDLVFRPRPRQ{PHURUHVLGXDO
SODVWLILFDQWHVDQWLR[LGDQWHVHVROYHQWHVUHVLGXDLVHPDGHVLYRVHWLQWDV
 $FRPSDQKDPHQWRGDFLQpWLFDGHXPDUHDomRGHSROLPHUL]DomR$FURPDWRJUDILD
JDVRVD SHUPLWH TXDQWLILFDU R PRQ{PHUR UHVLGXDO D FDGD WHPSR DR ORQJR GD
SROLPHUL]DomR 3DUD WDQWR p QHFHVViULD D XWLOL]DomR GH XP SDGUmR LQWHUQR TXH
QmR LQWHUILUD QR SURFHVVR GH SROLPHUL]DomR $ FRQFHQWUDomR GR PRQ{PHUR p
FRPSDUDGDjFRQFHQWUDomRGRSDGUmRDFDGDWHPSR
 3LUyOLVH GR SROtPHUR H FDUDFWHUL]DomR GH VXD HVWUXWXUD 3DUD HVWH FDVR p
QHFHVViULRXPSLUROLVDGRUDFRSODGRDRFURPDWyJUDIRDJiV$DOWDWHPSHUDWXUDGR
SLUROLVDGRUJHUDIUDJPHQWRVGDPDFURPROpFXODFRPSUHVVmRGHYDSRUVXILFLHQWH
SDUD VHUHP FDUUHDGRV SHOD IDVH PyYHO (VWDV SHTXHQDV PROpFXODV RULJLQDGDV GD
GHFRPSRVLomRGRSROtPHURSDVVDPSHODFROXQDFURPDWRJUiILFD2FURPDWRJUDPD

 &URPDWRJUDILD
REWLGRDSDUWLUGHVWDWpFQLFDpGHQRPLQDGRSLURJUDPDHVXDIRUPDGHSHQGHGDV
FDUDFWHUtVWLFDV HVWUXWXUDLV GR SROtPHUR WDLV FRPR VHTrQFLD GH PRQ{PHURV
HVWHUHRUUHJXODULGDGHJUDXGHUDPLILFDomRRXUHWLFXODomRFULVWDOLQLGDGHHWF
 $QiOLVH GR SROtPHUR FRPR IDVH HVWDFLRQiULD (VWD WpFQLFD p GHQRPLQDGD
FURPDWRJUDILD JDVRVD LQYHUVD RQGH R SROtPHUR D VHU DQDOLVDGR FRQVWLWXL D IDVH
HVWDFLRQiULD1HVWHFDVRVmRPHGLGDVDVLQWHUDo}HVGRSROtPHURFRPXPVROXWR
FRQKHFLGRFDUUHDGRQDIDVHPyYHO(VWHWLSRGHFURPDWRJUDILDVHUiDSUHVHQWDGRD
VHJXLU

7.3.4 Cromatografia gasosa inversa


7.3.4.1 Princpio terico
$ FURPDWRJUDILD JDVRVD LQYHUVD p XPD WpFQLFD FURPDWRJUiILFD TXH HPSUHJD XP
SROtPHUR FRPR IDVH HVWDFLRQiULD H R TXH VH PHGH VmR DV LQWHUDo}HV GHVWD IDVH
HVWDFLRQiULDFRPRVROXWRYROiWLOFRQKHFLGR$SDUWLUGDIRUoDGHVWDVLQWHUDo}HVHGD
VXD GHSHQGrQFLD FRP D WHPSHUDWXUD p SRVVtYHO DYDOLDU DV SURSULHGDGHV GH XP
VLVWHPDSROtPHURVROXWRRXPHVPRGRSROtPHURSXUR
2VGDGRVGHUHWHQomRGRVROXWRVmRGHWHUPLQDGRVDSDUWLUGRYROXPHGHUHWHQomR
HVSHFtILFR 9J FRUULJLGRD&FRPRH[SUHVVRQD(TXDomR

273,2 VR 273,2
Vg = = K (7.6)
T w T
RQGH 95 p R YROXPH GH UHWHQomR j WHPSHUDWXUD DEVROXWD 7  Z p D PDVVD GD IDVH
HVWDFLRQiULD GD FROXQD H . p R FRHILFLHQWH GH GLVWULEXLomR GR VROXWR HQWUH D IDVH
HVWDFLRQiULDHDIDVHPyYHO
2GLDJUDPDGHUHWHQomRpREWLGRFRORFDQGRVHHPJUiILFRRORJDULWPRGRYROXPH
GH UHWHQomR HVSHFtILFR 9J  YHUVXV R LQYHUVR GD WHPSHUDWXUD DEVROXWD $ )LJXUD 
LOXVWUD HVWD GHSHQGrQFLD SDUD XPD DPRVWUD GH XP SROtPHUR VHPLFULVWDOLQR 2
GLDJUDPDGHUHWHQomRpOLQHDUHDVXDLQFOLQDomRpUHODFLRQDGDjHQWDOSLDGDVROXomR
QD IDVH OtTXLGD HVWDFLRQiULD FURPDWRJUDILD JiVOtTXLGR  RX j DGVRUomR HP XPD
VXSHUItFLHVyOLGD FURPDWRJUDILDJiVVyOLGR GHDFRUGRFRPD(TXDomR
ln V g H
=
1( )
T
R
(7.7)

RQGH+pDHQWDOSLDGDVROXomRH5pDFRQVWDQWHXQLYHUVDOGRVJDVHV

&DUDFWHUL]DomRGH3ROtPHURV 
)LJXUD'LDJUDPDGHUHWHQomRSDUDXPDDPRVWUDGHXPSROtPHURVHPLFULVWDOLQR 

7.3.4.2 Aplicaes da cromatografia gasosa inversa na caracterizao e


anlise de polmeros
$V SULQFLSDLV DSOLFDo}HV GD FURPDWRJUDILD JDVRVD LQYHUVD QR HVWXGR GH SROtPHURV
VmR
SHVWXGRGRPHFDQLVPRGHUHWHQomRHPXPSROtPHURVyOLGR
SGHWHUPLQDomRGDWHPSHUDWXUDGHWUDQVLomRYtWUHD 7J HGDWHPSHUDWXUDGHIXVmR
FULVWDOLQD 7P 
SHVWXGRVWHUPRGLQkPLFRVGHVROXo}HVSROLPpULFDV
SGHWHUPLQDomRGDFULVWDOLQLGDGHGHXPDIDVHHVWDFLRQiULDSROLPpULFD
SGHWHUPLQDomRGRFRHILFLHQWHGHGLIXVmR
SHVWXGRVVREUHDVSURSULHGDGHVVXSHUILFLDLVGHXPSROtPHUR
SGHWHUPLQDomRGHSDUkPHWURVGHVROXELOLGDGHHGHLQWHUDomR)ORU\+XJJLQV 
SPLFURVHSDUDomRGHIDVHVHWDPDQKRGRVGRPtQLRVGHFRSROtPHURVHPEORFR
SGHWHUPLQDomRGRJUDXGHOLJDo}HVFUX]DGDV
$VLQIRUPDo}HVTXHSRGHPVHUREWLGDVDSDUWLUGDFURPDWRJUDILDJDVRVDLQYHUVD
VmRLOXVWUDGDVQRGLDJUDPDGHUHWHQomRDSUHVHQWDGRQD)LJXUD

 &URPDWRJUDILD
 6HJPHQWR $%  QHVWD UHJLmR GH WHPSHUDWXUD R SROtPHUR HVWi DEDL[R GH VXD
WHPSHUDWXUDGHWUDQVLomRYtWUHD$SHQHWUDomRGDVPROpFXODVGRVROXWRGHQWURGD
IDVH SROLPpULFD p LPSHGLGD $ UHWHQomR RFRUUH SULQFLSDOPHQWH GHYLGR jV
DGVRUo}HV VXSHUILFLDLV H R GLDJUDPD GH UHWHQomR p OLQHDU QHVWD UHJLmR 1HVWH
VHJPHQWR REWpPVH HQWmR LQIRUPDo}HV VREUH DV SURSULHGDGHV VXSHUILFLDLV GR
SROtPHUR
 3RQWR %  HVWH SRQWR FRUUHVSRQGH j WHPSHUDWXUD GH WUDQVLomR YtWUHD 7J  $V
FDGHLDV SROLPpULFDV TXH FRQVWLWXHP D IDVH HVWDFLRQiULD DGTXLUHP PDLRU
PRELOLGDGHDXPHQWDQGRDSRVVLELOLGDGHGHSHQHWUDomRGDVPROpFXODVGRVROXWR
GHQWUR GD PDVVD SROLPpULFD ,VWR ID] FRP TXH R YROXPH GH UHWHQomR HVSHFtILFR
DXPHQWHFRPDWHPSHUDWXUD
 6HJPHQWR %&  QHVWD UHJLmR GH WHPSHUDWXUD R FRHILFLHQWH GH GLIXVmR GR VROXWR
GHQWURGDPDVVDSROLPpULFDDXPHQWDFRPRDXPHQWRGDWHPSHUDWXUD
 3RQWR&QHVWHSRQWRRSURFHVVRGHGLIXVmRDWLQJHRHTXLOtEULR
 6HJPHQWR&'QHVWDUHJLmRGHWHPSHUDWXUD TXHHVWiDEDL[RGDWHPSHUDWXUDGH
IXVmRGRSROtPHUR DUHWHQomRRFRUUHGHYLGRjVRUomRGRVROXWRGHQWURGDPDVVD
SROLPpULFD$VLQWHUDo}HVSROtPHURVROXWRVmRUHVWULWDVDRVGRPtQLRVDPRUIRVGD
IDVHSROLPpULFDHVWDFLRQiULD
 6HJPHQWR')QHVWDUHJLmRGHWHPSHUDWXUDH[DWDPHQWHDEDL[RGDWHPSHUDWXUD
GHIXVmRDIUDomRGDIDVHDPRUIDDXPHQWDRFDVLRQDQGRXPDXPHQWRQRYROXPH
GHUHWHQomR
 3RQWR)HVWHSRQWRFRUUHVSRQGHDRSRQWRGHIXVmR
 6HJPHQWR)*QHVWDUHJLmRDFLPDGD7PRFRUUHDVRUomRGRVROXWRGHQWURGDIDVH
SROLPpULFD FRPSOHWDPHQWH DPRUID H R GLDJUDPD GH UHWHQomR p OLQHDU
([WUDSRODQGRVH HVWD OLQKD D EDL[DV WHPSHUDWXUDV D SRUomR FULVWDOLQD GD IDVH
HVWDFLRQiULD SRGH VHU GHWHUPLQDGD FRPSDUDQGRVH R YROXPH GH UHWHQomR
H[SHULPHQWDOFRPRYDORUOLGRQDH[WUDSRODomR1HVWDUHJLmR)*RSROtPHURHVWi
FRPSOHWDPHQWH DPRUIR H DV SURSULHGDGHV UHODFLRQDGDV DR SDU SROtPHURVROXWR
SRGHPVHULQYHVWLJDGDV

SDeterminao da temperatura de transio vtrea


$GHWHUPLQDomRGDWHPSHUDWXUDGHWUDQVLomRYtWUHD 7J GRSROtPHURTXHFRQVWLWXLD
IDVHHVWDFLRQiULDpEDVHDGDQDVPXGDQoDVHQWUHDVDGVRUo}HVVXSHUILFLDLVDEDL[RGD
7J H D VRUomR GHQWUR GD PDVVD SROLPpULFD TXH RFRUUH DFLPD GD 7J )LJXUD   $
PXGDQoDREVHUYDGDQRPHFDQLVPRGHUHWHQomRQD7JpXPUHVXOWDGRGRDXPHQWRGD
PRELOLGDGH PROHFXODU GRV VHJPHQWRV SROLPpULFRV TXH RFRUUH QHVWD WHPSHUDWXUD H
DFLPD GHVWD (VWH DXPHQWR GD PRELOLGDGH SHUPLWH D SHQHWUDomR GH PROpFXODV GR
VROXWRGHQWURGDPDVVDSROLPpULFD

&DUDFWHUL]DomRGH3ROtPHURV 
1DGHWHUPLQDomRGDWUDQVLomRYtWUHDRVROXWRSUHFLVDVHUXPQmRVROYHQWHSDUDR
SROtPHUR SDUD TXH VH SRVVD REVHUYDU R UHYHUVR GR FRPSRUWDPHQWR OLQHDU 3DUD
PD[LPL]DUDLQGDPDLVDSDUWHUHYHUVDGDFXUYDRFRHILFLHQWHGHSDUWLomRGDPDVVD
SROLPpULFDGHYHVHURPDLRUSRVVtYHOHRFRHILFLHQWHGHSDUWLomRVXSHUILFLDORPHQRU
SRVVtYHO

SDeterminao da cristalinidade de um polmero


$ GHWHUPLQDomR GD FULVWDOLQLGDGH GH SROtPHURV QD IDVH HVWDFLRQiULD p EDVHDGD QD
VROXELOLGDGHGLIHUHQFLDOGRVROXWRQRVGRPtQLRVFULVWDOLQRVHDPRUIRVGRSROtPHUR$
VROXELOLGDGHGHWRGRVRVVROXWRVQRVFULVWDLVpEHPPHQRUGRTXHHPOtTXLGRVHP
IXQGLGRV RX HP ERUUDFKDV GH PHVPD HVWUXWXUD PROHFXODU  3RUWDQWR D UHWHQomR
UHGX]LGDQRVSROtPHURVFULVWDOLQRVpGHYLGDjEDL[DVROXELOLGDGHGRVROXWRQDUHJLmR
FULVWDOLQD$VLQWHUDo}HVSROtPHURVROXWRVmRUHVWULWDVDRVGRPtQLRVDPRUIRV&RPR
GHFUpVFLPR GD FULVWDOLQLGDGH R YROXPH GH UHWHQomR HVSHFtILFR DXPHQWD GHYLGR DR
DXPHQWRGDIDVHDPRUIDRQGHRVROXWRSRGHSHQHWUDU
$ FULVWDOLQLGDGH GH XP SROtPHUR VHPLFULVWDOLQR SRGH VHU GHWHUPLQDGD
TXDQWLWDWLYDPHQWH D SDUWLU GR GLDJUDPD GH UHWHQomR 9ROWDQGR D DQDOLVDU D FXUYD
DSUHVHQWDGD QD )LJXUD  YHULILFDVH TXH DFLPD GR SRQWR GH IXVmR SRQWR )  R
SROtPHUR p FRPSOHWDPHQWH DPRUIR H XP GLDJUDPD GH UHWHQomR OLQHDU p REWLGR
VHJPHQWR )*  ([WUDSRODQGRVH D OLQKD UHWD GR VHJPHQWR )* SDUD WHPSHUDWXUDV
PDLV EDL[DV REWpPVH R YROXPH GH UHWHQomR WHyULFR FRQVLGHUDQGRVH R SROtPHUR
WHRULFDPHQWHDPRUIR
2JUDXGDIUDomRDPRUID ;D GDIDVHHVWDFLRQiULDSROLPpULFDSRGHVHUFDOFXODGRD
SDUWLUGD(TXDomR
Vg
Xa =
V g (7.8)

RQGH9JpRYDORUGRYROXPHGHUHWHQomRUHDOPHGLGRH9
JpRYDORUGRYROXPHGH
UHWHQomRTXHVHULDH[LELGRVHDDPRVWUDIRVVHFRPSOHWDPHQWHDPRUID2EYLDPHQWH
DPERVGHYHPVHUPHGLGRVDXPDPHVPDWHPSHUDWXUD
2 JUDX GH FULVWDOLQLGDGH ;F  GD IDVH HVWDFLRQiULD REWLGR HP SRUFHQWDJHP SRGH
VHUFDOFXODGRGHDFRUGRFRPD(TXDomR
V
X c = 1001 g (7.9)
V g
2 JUDX GH FULVWDOLQLGDGH Pi[LPR SRVVtYHO ;FPD[  D XPD GDGD WHPSHUDWXUD p
IRUQHFLGRSHOD(TXDomR

 &URPDWRJUDILD
V
X c , max = 1001 g (equil ) (7.10)
V g

RQGH 9J HTXLO  p R YROXPH GH UHWHQomR GR SROtPHUR QR SRQWR GH HTXLOtEULR HQWUH DV
IDVHVDPRUIDHFULVWDOLQD

SDeterminao do coeficiente de difuso de um polmero


2SURFHVVRGHGLIXVmRHPXPDFROXQDFURPDWRJUiILFDRFDVLRQDXPDODUJDPHQWRGR
SLFR2FRHILFLHQWHGHGLIXVmRGHXPVROXWRQDIDVHSROLPpULFDHVWDFLRQiULDSRGHVHU
HQWmR GHWHUPLQDGR D SDUWLU GD ODUJXUD GR SLFR UHIHUHQWH DR FRPSRQHQWH HOXtGR 2
DODUJDPHQWRGRSLFRpXPDIXQomRGDVSURSULHGDGHVGDFROXQDHSRGHVHUH[SUHVVR
HPWHUPRVGDDOWXUDHTXLYDOHQWHDRSUDWRWHyULFR +(73 
HETP = A + B v + Cv (7.11)

RQGHYpDYD]mRGHIOX[RGRJiVFDUUHDGRUQDFROXQD$pXPDFRQVWDQWHHPStULFD
TXHOHYDHPFRQVLGHUDomRRDODUJDPHQWRGDEDQGDGHYLGRDRSUySULRLQVWUXPHQWR
%pDGLIXVmRPROHFXODUH&pXPDFRQVWDQWHUHODFLRQDGDDRWHPSRILQLWRQHFHVViULR
SDUD VH DOFDQoDU R HTXLOtEULR QD IDVH HVWDFLRQiULD TXH FRUUHVSRQGH j WUDQVIHUrQFLD
GHPDVVD
$FRQVWDQWH&pFDOFXODGDXWLOL]DQGRVHD(TXDomR

8d 2 K
C= 2
D1 (1 + K )2 (7.12)

RQGHGpDHVSHVVXUDGDIDVHHVWDFLRQiULD'pRFRHILFLHQWHGHGLIXVmRGRVROXWRQR
SROtPHUR H . p R FRHILFLHQWH GH GLVWULEXLomR FRHILFLHQWH GH SDUWLomR  GHWHUPLQDGR
VHJXQGRD(TXDomR
(t R t M )
K= (7.13)
tM
RQGHW5HW0FRUUHVSRQGHPUHVSHFWLYDPHQWHDRVWHPSRVGHUHWHQomRSDUDRVROXWRH
SDUDXPDVXEVWkQFLDDTXDOQmRLQWHUDJHFRPDFROXQD
2 YDORU GH +(73 SRGH VHU GHWHUPLQDGR D SDUWLU GD ODUJXUD GRV SLFRV GR VROXWR
HOXtGRDYiULDVYHORFLGDGHVGHIOX[RGRJiV$FRQVWDQWH&SRGHVHUREWLGDDSDUWLUGD
LQFOLQDomR GD FXUYD GH +(73 YHUVXV Y (VWD GHSHQGrQFLD WRUQDVH OLQHDU TXDQGR VH
XWLOL]DP DOWDV YHORFLGDGHV GH IOX[R RX VHMD TXDQGR D UD]mR %Y GD HTXDomR 

&DUDFWHUL]DomRGH3ROtPHURV 
WHQGH D ]HUR $ SDUWLU GRV YDORUHV FRQKHFLGRV GH G H . R FRHILFLHQWH GH GLIXVmR '
SRGHVHUFDOFXODGR
$ GHWHUPLQDomR GR FRHILFLHQWH GH GLIXVmR p WDPEpP XVDGD QD FURPDWRJUDILD
JDVRVDFRQYHQFLRQDO

7.3.4.3 Preparao de uma coluna capilar


&ROXQDVGHDoRLQR[LGiYHOGHYHPVHUFXLGDGRVDPHQWHOLPSDVDQWHVGDDSOLFDomRGR
ILOPHGHSROtPHURQDSDUHGHLQWHUQD$HVSHVVXUDGRILOPHGHSROtPHURGHYHHVWDUQD
IDL[DcHQRUPDOPHQWHXWLOL]DVHXPPpWRGRGLQkPLFRGHDSOLFDomR1HVWH
PpWRGRFHUFDGHP/GHXPDVROXomRSROLPpULFD GHFRQFHQWUDomRQDIDL[DGHD
HPSHVR VmRFRORFDGRVHPXPUHVHUYDWyULRHHPSXUUDGRVSDUDDFROXQDSRU
PHLR GH XP IOX[R GH QLWURJrQLR (VWH IOX[R GH QLWURJrQLR FRQWtQXR RFDVLRQD D
HYDSRUDomRGRVROYHQWHQDVROXomRORFDOL]DGDGHQWURGDFROXQDGDQGRRULJHPDXP
ILOPH SROLPpULFR DGHULGR jV SDUHGHV LQWHUQDV 3DUD VH DWLQJLU XPD HVSHVVXUD
DGHTXDGD GHVWH ILOPH p QHFHVViULR XP QRYR ERPEHDPHQWR GH  P/ GD VROXomR
SROLPpULFD(VWHSURFHVVRpUHSHWLGRWDQWDVYH]HVTXDQWDVIRUHPQHFHVViULDVSDUDVH
DWLQJLU D HVSHVVXUD GHVHMDGD $ TXDQWLGDGH GH SROtPHUR QD FROXQD p GHWHUPLQDGD
SHVDQGRVHDFROXQDDQWHVHDSyVRUHFREULPHQWR$)LJXUDLOXVWUDRSURFHVVRGH
UHFREULPHQWRLQWHUQRGHXPDFROXQDFDSLODUFRPXPDIDVHOtTXLGD

)LJXUD(VTXHPDLOXVWUDWLYRGRPpWRGRGLQkPLFRXWLOL]DGRSDUDUHFREULPHQWRLQWHUQRGHFROXQDV
FDSLODUHVXWLOL]DQGRXPDIDVHOtTXLGD

 &URPDWRJUDILD
([LVWH DLQGD RXWUR WLSR GH FROXQD HP TXH R SROtPHUR p GHSRVLWDGR VREUH
SDUWtFXODVGHVtOLFD RXRXWURWLSRGHVXSRUWH DVTXDLVVHUmRXWLOL]DGDVSDUDUHFKHDU
DFROXQDGHDoRLQR[LGiYHO

7.4 Cromatografia lquida


$ FURPDWRJUDILD OtTXLGD XWLOL]D XP OtTXLGR FRPR IDVH PyYHO 'HSHQGHQGR GD
QDWXUH]D GD IDVH HVWDFLRQiULD D VHSDUDomR DFRQWHFH D SDUWLU GH PHFDQLVPRV
GLIHUHQWHV
 &URPDWRJUDILD GH SDUWLomR  (VWH WLSR GH FURPDWRJUDILD p FRQVLGHUDGR FRPR
OtTXLGROtTXLGRRQGHDDPRVWUDpGLVWULEXtGDHQWUHGRLVOtTXLGRVLPLVFtYHLVTXH
FRQVWLWXHPDIDVHPyYHOHDIDVHHVWDFLRQiULD
 &URPDWRJUDILD GH DGVRUomR  (VWD WpFQLFD FURPDWRJUiILFD p FRQVLGHUDGD GR WLSR
OtTXLGRVyOLGRRQGHDIDVHPyYHOpXPOtTXLGRHDIDVHHVWDFLRQiULDpXPVyOLGR
 &URPDWRJUDILDGHWURFDL{QLFD(VWDWpFQLFDGHSHQGHGDFDSDFLGDGHGHDGVRUomR
GRVtRQVHQWUHDIDVHPyYHOHRVVtWLRVL{QLFRVGRVXSRUWH
 &URPDWRJUDILDGHH[FOXVmRSRUWDPDQKR(VWDWpFQLFDXWLOL]DJHOSROLPpULFRQmR
L{QLFRFRPDOWDSRURVLGDGHFRPRIDVHHVWDFLRQiULD

$FURPDWRJUDILDOtTXLGDGRWLSROtTXLGRVyOLGRSRGHVHUGHGHVHQYROYLPHQWRRX
GHHOXLomR
$&URPDWRJUDILDGHGHVHQYROYLPHQWRRXFURPDWRJUDILDGHFDPDGDILQD 7/& XWLOL]D
XPDFDPDGDILQDGHXPVyOLGRFRPRIDVHHVWDFLRQiULDHVSDOKDGDHPXPDVXSHUItFLH
SODQD SRUH[HPSOROkPLQDGHYLGUR 
$&URPDWRJUDILDGHHOXLomRXWLOL]DXPDFROXQDUHFKHDGDFRPDIDVHHVWDFLRQiULD
VHQGR D IDVH PyYHO HOXtGD DWUDYpV GD FROXQD $ FURPDWRJUDILD GH HOXLomR SRGH VHU
UHDOL]DGDUHFKHDQGRVHXPDFROXQDGHYLGURFRPXPVXSRUWHDSURSULDGR VtOLFDRX
DOXPLQD VHQGRDIDVHPyYHOHOXtGDOHQWDPHQWHDWUDYpVGHVWDFROXQD
3DUDH[SHULPHQWRVHPODERUDWyULRXWLOL]DVHDWpFQLFDGHVHSDUDomRSRUDGVRUomR
WDQWR SDUD D FURPDWRJUDILD GH FDPDGD ILQD 7/&  FRPR SDUD D FURPDWRJUDILD GH
HOXLomRXPDYH]TXHDIDVHHVWDFLRQiULDXWLOL]DGDSRGHVHUIDFLOPHQWHDSOLFDGDWDQWR
QDVXSHUItFLHGRYLGURRXFRORFDGDHPXPDFROXQD
$QiOLVHV PDLV HODERUDGDV HQYROYHQGR D FURPDWRJUDILD OtTXLGD UHTXHUHP
HTXLSDPHQWRV HVSHFLDLV TXH IRUQHFHP UHVXOWDGRV PDLV SUHFLVRV HP WHPSRV EHP
PHQRUHV (VWHV HTXLSDPHQWRV VmR GHQRPLQDGRV FURPDWyJUDIRV OtTXLGRV GH DOWD
HILFLrQFLD +3/&  &RPR YHUHPRV D VHJXLU DOpP GD VHSDUDomR GH VXEVWkQFLDV WDLV
HTXLSDPHQWRV SRVVXHP UHFXUVRV TXH SHUPLWHP XPD VpULH GH RXWUDV LQIRUPDo}HV
LPSRVVtYHLV GH VHUHP DGTXLULGDV HP XPD VLPSOHV HOXLomR HP FROXQD UHDOL]DGD HP
ODERUDWyULR

&DUDFWHUL]DomRGH3ROtPHURV 
7.4.1 Descrio do cromatgrafo lquido de alta eficincia
2HTXLSDPHQWRXWLOL]DGRQDFURPDWRJUDILDOtTXLGDpFRPXPSDUDWRGRVRVWLSRVGH
FURPDWRJUDILD OtTXLGD GH DOWD UHVROXomR +3/&  SDUWLomR DGVRUomR H H[FOXVmR SRU
WDPDQKR $VGLIHUHQoDVHQWUHHVWHVPpWRGRVVmRJRYHUQDGDVSHODQDWXUH]DGDIDVH
HVWDFLRQiULDFRPRYHUHPRVPDLVWDUGH$)LJXUDDSUHVHQWDXPGLDJUDPDGHXP
FURPDWyJUDIROtTXLGR

)LJXUD'LDJUDPDHVTXHPiWLFRGHXPFURPDWyJUDIROtTXLGR

(OHpFRQVWLWXtGRGDVVHJXLQWHVSDUWHV
 )DVHPyYHO
 %RPEDSHULVWiOWLFD
 6LVWHPDGHLQMHomRGDDPRVWUD
 &ROXQDV IDVHHVWDFLRQiULD 
 'HWHFWRUHV
 6LVWHPDGHDTXLVLomRGHGDGRV

7.4.1.1 Fase mvel


$ IDVH PyYHO p FRQVWLWXtGD SRU XP OtTXLGR FDSD] GH GLVVROYHU FRPSOHWDPHQWH D
VXEVWkQFLD D VHU DQDOLVDGD 2 VROYHQWH XWLOL]DGR FRPR IDVH PyYHO GHYH VHU
FRPSDWtYHO FRP D IDVH HVWDFLRQiULD H WDPEpP FRP RV GHWHFWRUHV XWLOL]DGRV 2
UHVHUYDWyULR FRQWHQGR D IDVH PyYHO GHYH VHU UHODWLYDPHQWH JUDQGH SDUD HYLWDU

 &URPDWRJUDILD
TXDOTXHU GLVW~UELR QRV VLVWHPDV GH GHWHFWRUHV $ IDVH PyYHO GHYH HVWDU OLYUH GH
SDUWtFXODVSDUDQmRSUHMXGLFDUDIDVHHVWDFLRQiULDHOLYUHGHJDVHVDGVRUYLGRV

7.4.1.2 Bomba peristltica


$ ERPED SHULVWiOWLFD WHP D IXQomR GH FRQGX]LU R VROYHQWH IDVH PyYHO  GR
UHVHUYDWyULR SDUD WRGR R VLVWHPD (OD SURSRUFLRQD XPD YD]mR FRQVWDQWH H
UHSURGXWtYHO GR IOX[R VLVWHPD GH GHVORFDPHQWR FRQVWDQWH  2 VLVWHPD GH
ERPEHDPHQWR GR VROYHQWH p IHLWR DWUDYpV GH SLVW}HV GH VDILUD TXH WUDEDOKDP HP
PRYLPHQWRDOWHUQDGR3DUDTXHHVWHVLVWHPDGHERPEHDPHQWRQmRVHMDSUHMXGLFDGR
pLPSRUWDQWHDDXVrQFLDGHEROKDVGHDUHPDWHULDLVHPVXVSHQVmR
2 VLVWHPD GH ERPEHDPHQWR H DV WXEXODo}HV GHYHP VHU OLPSRV SHULRGLFDPHQWH
GDVHJXLQWHIRUPD
SUHWLUDPVHDVFROXQDVGRVLVWHPD
SERPEHLDVHiFLGRDFpWLFRRXXPDVROXomRGHiFLGRQtWULFRHiJXDQDSURSRUomR
YY
SERPEHLDVHiJXDDWpTXHDiJXDGHVDtGDDSUHVHQWHS+QHXWUR
SERPEHLDVHPHWDQROHHPVHJXLGDRVROYHQWHQRUPDOPHQWHXWLOL]DGRFRPRIDVH
PyYHO

7.4.1.3 Sistema de injeo


$ DPRVWUD p LQWURGX]LGD QR VLVWHPD FURPDWRJUiILFR XWLOL]DQGRVH XPD VHULQJD TXH
DWUDYHVVDXPVHSWRGHERUUDFKD$QWHVGDDPRVWUDHQWUDUQRIOX[RGDIDVHPyYHOHOD
ILFD DUPD]HQDGD QR LQMHWRU 2 LQMHWRU PDLV XWLOL]DGR DWXDOPHQWH p DTXHOH GR WLSR
5KHRG\QH (VWH LQMHWRU FRQVWLWXtGR GH XPD YiOYXOD FRP VDtGDV P~OWLSODV H XP
VHJPHQWRGRWLSRORRSpDSUHVHQWDGRQD)LJXUD
&RPRLQMHWRUQDSRVLomRFDUUHJDUDVROXomRGDDPRVWUDpLQMHWDGD(VWDVROXomR
SHUPDQHFH QR UHVHUYDWyULR SHTXHQR ORRS  HQTXDQWR TXH R VROYHQWH p
FRQVWDQWHPHQWHERPEHDGRSDUDDVFROXQDVVHPDUUDVWDUDDPRVWUDDVHUDQDOLVDGD
6HRYROXPHGDVROXomRLQMHWDGDIRUPDLRUGRTXHDFDSDFLGDGHGRORRSRUHVWRGD
VROXomRpHOLPLQDGRFRPRUHMHLWR
4XDQGR R VLVWHPD GH LQMHomR p DFLRQDGR SRVLomR LQMHWDU  R VROYHQWH ERPEHDGR
PXGDRVHXFDPLQKRHSDVVDSHORORRSFRORFDQGRDDPRVWUDQRIOX[RGRVROYHQWH
TXHDFRQGX]LUiDWpDVFROXQDV

&DUDFWHUL]DomRGH3ROtPHURV 
)LJXUD6LVWHPDGHLQMHomRGRWLSR5KHRG\QH

7.4.1.4 Fase estacionria


$IDVHHVWDFLRQiULDFRQVWLWXLRUHFKHLRGDVFROXQDV$QDWXUH]DGDIDVHHVWDFLRQiULD
LUiGHWHUPLQDURPHFDQLVPRGDVHSDUDomRFRPRGLVFXWLUHPRVSRVWHULRUPHQWH(ODp
FRQVWLWXtGD GH SDUWtFXODV HPSDFRWDGDV HP XPD FROXQD GH DoR LQR[LGiYHO (VWDV
SDUWtFXODVGHYHPDSUHVHQWDUXPDVpULHGHFDUDFWHUtVWLFDVWDLVFRPR
 DOWDSRURVLGDGHHVSHFtILFDLVWRpDOWRYROXPHGHSRURSRUXQLGDGHGHSHVRRTXH
DXPHQWDDHILFLrQFLDGDVHSDUDomR
 WDPDQKRGHSRURVFRPSDWtYHOFRPDVXEVWkQFLDDVHUVHSDUDGD
 D GLIXVmR GDV PDFURPROpFXODV GHQWUR GDV SDUWtFXODV GR UHFKHLR QmR SRGH VHU
PXLWRGLItFLOHRWDPDQKRGDVSDUWtFXODVGHYHVHUUHODWLYDPHQWHSHTXHQR
 D IRUPD GDV SDUWtFXODV GHYH VHU HVIpULFD H VXD GLVWULEXLomR GH WDPDQKR D PDLV
HVWUHLWDSRVVtYHO

3DUD TXH D IDVH HVWDFLRQiULD DSUHVHQWH XP ERP GHVHPSHQKR H XPD YLGD ~WLO
ORQJDpQHFHVViULRWRPDUGHWHUPLQDGRVFXLGDGRVUHODFLRQDGRVDVHJXLU
S8VDUVROYHQWHFRPSDWtYHOFRPDQDWXUH]DGRUHFKHLRSRUH[HPSORiJXDHRXWURV
VROYHQWHV PXLWR SRODUHV QmR SRGHP VHU XWLOL]DGRV TXDQGR D IDVH HVWDFLRQiULD p
KLGURIyELFD

 &URPDWRJUDILD
S2EVHUYDU RV OLPLWHV GH SUHVVmR SDUD TXH DV SDUWtFXODV PDQWHQKDP D VXD
HVWDELOLGDGHGLPHQVLRQDO
S7RPDU FXLGDGR FRP D WURFD GH VROYHQWH  D WURFD GH VROYHQWH p FRPXP HP
FURPDWRJUDILD GH DGVRUomR SRUpP GHYH VHU HYLWDGD HP FURPDWRJUDILD GH
H[FOXVmRSRUWDPDQKR
S3DUD XPD DQiOLVH FURPDWRJUiILFD j WHPSHUDWXUD DPELHQWH D FROXQD GHYH VHU
PDQWLGDDXPDWHPSHUDWXUDHQWUHH&DILPGHGLPLQXLUDYLVFRVLGDGHGD
IDVHPyYHOHFRPLVVRGLPLQXLUDSUHVVmRGRVLVWHPD
S8VDU XP IOX[R DGHTXDGR SDUD FDGD WLSR GH UHFKHLR 3DUD UHFKHLRV TXH VRIUHP
DOJXP WLSR GH LQFKDPHQWR FRP VROYHQWH R IOX[R QmR SRGH VHU YDULDGR
EUXVFDPHQWH

2V VXSRUWHV XWLOL]DGRV FRPR IDVH HVWDFLRQiULD SRGHP VHU FRQVWLWXtGRV GH
PDWHULDLVSRURVRVLQRUJkQLFRVRXSROtPHURVUHWLFXODGRV
0DWHULDLV SRURVRV LQRUJkQLFRV SRVVXHP SRURVLGDGH SHUPDQHQWH RX VHMDP QmR
VRIUHP LQFKDPHQWR QD SUHVHQoD GD IDVH PyYHO 6mR QRUPDOPHQWH FRQVWLWXtGRV GH
VtOLFD JHO H YLGUR FRP SRURVLGDGH FRQWURODGD 7HUUD GLDWRPiFHD H DOXPLQD WDPEpP
VmRXWLOL]DGDVFRPRUHFKHLR
3ROtPHURVUHWLFXODGRVVRIUHPLQFKDPHQWRQDSUHVHQoDGDIDVHPyYHO2JUDXGH
LQFKDPHQWR GHSHQGH GD QDWXUH]D GD IDVH HVWDFLRQiULD H GD IDVH PyYHO 'HQWUH RV
SROtPHURVUHWLFXODGRVHPSUHJDGRVFRPRIDVHHVWDFLRQiULDGHVWDFDPVH
SJHO UtJLGR RUJkQLFR  FRQVWLWXtGR GH SROLHVWLUHQR UHWLFXODGR TXH LQFKD OLJHLUD
PHQWHQDSUHVHQoDGHVROYHQWH
SUHGHVLVRSRURVDVWDPEpPFRQVWLWXtGDGHSROLHVWLUHQRUHWLFXODGR VmRFKDPDGDV
LVRSRURVDV SRUTXH D GHQVLGDGH GH UHWLFXODomR p KRPRJrQHD H HQWmR D GLVWUL
EXLomRGRWDPDQKRGHSRURVpHVWUHLWD 
SJHOQDWXUDOUHYHUVtYHO FRPRDDJDURVH HJHOIOH[tYHO FRPRDSROLDFULODPLGDOLJHL
UDPHQWHUHWLFXODGD DPERVLQFKDPEDVWDQWHQDSUHVHQoDGHERQVVROYHQWHV$
SRURVLGDGHGHVWHVUHFKHLRVpHVWDEHOHFLGDSHORLQFKDPHQWR

7.4.1.5 Detectores
2GHWHFWRUpRFRPSRQHQWHGRVLVWHPDFURPDWRJUiILFRTXHIRUQHFHRVLQDOGHYLGRj
SUHVHQoDGDDPRVWUDQRIOX[RGDIDVHPyYHO(OHpFRQHFWDGRQDVDtGDGDFROXQDSDUD
PRQLWRUDU R HIOXHQWH GD FROXQD QR WHPSR UHDO ([LVWHP YiULRV WLSRV GH GHWHFWRUHV
WDLVFRPR
StQGLFHGHUHIUDomR
SHVSHFWU{PHWURGHXOWUDYLROHWD
SHVSHFWU{PHWURGHLQIUDYHUPHOKR
SIOXRUHVFrQFLD

&DUDFWHUL]DomRGH3ROtPHURV 
SYLVFRVLPpWULFR
SHVSDOKDPHQWR de luz.

2V PDLV FRPXQV VmR DTXHOHV EDVHDGRV QR tQGLFH GH UHIUDomR H QD DEVRUomR QD
UHJLmR GR XOWUDYLROHWD 1R FDVR GH DQiOLVH GH SHVR PROHFXODU GH SROtPHURV SRU
FURPDWRJUDILD GH H[FOXVmR SRU WDPDQKR XWLOL]DPVH WDPEpP FRP JUDQGH
IUHTrQFLD RV GHWHFWRUHV EDVHDGRV HP PHGLGDV YLVFRVLPpWULFDV H HP PHGLGDV GH
HVSDOKDPHQWRGHOX]

SDetector de ndice de refrao


2 UHIUDW{PHWUR GLIHUHQFLDO p R GHWHFWRU PDLV XWLOL]DGR HP FURPDWRJUDILD OtTXLGD H
HP SDUWLFXODU QD FURPDWRJUDILD GH H[FOXVmR SRU WDPDQKR SRUTXH SUDWLFDPHQWH
WRGDVDVVROXo}HVSROLPpULFDVDSUHVHQWDPtQGLFHVGHUHIUDomRGLIHUHQWHVGDTXHOHVGR
VROYHQWHSXUR
2V GHWHFWRUHV PDLV VLPSOHV XWLOL]DP D GLIHUHQoD GH tQGLFHV GH UHIUDomR
REVHUYDGRVTXDQGRDOX]DWUDYHVVDXPDFpOXODFRQVWLWXtGDGHGRLVFRPSDUWLPHQWRV
$)LJXUDDSUHVHQWDXPHVTXHPDGDOX]UHIUDWDGDQHVWHWLSRGHFpOXOD2kQJXOR
UHSUHVHQWDRkQJXORGHGHIOH[mRTXHRIHL[HGHOX]VRIUHDSyVDWUDYHVVDURVGRLV
FRPSDUWLPHQWRV 4XDQGR RV GRLV FRPSDUWLPHQWRV VmR RFXSDGRV SHOR VROYHQWH
)LJXUDD REVHUYDVHXPkQJXORGHGHIOH[mRFRUUHVSRQGHQWHD$GLIHUHQoDQR
tQGLFH GH UHIUDomR FDXVDGD SHOD SUHVHQoD GD VROXomR GR SROtPHUR HP XP GRV
FRPSDUWLPHQWRV FDXVD XPD GHIOH[mR GR IHL[H GH OX] )LJXUD E  $ YDULDomR GR
kQJXOR  GHWHUPLQD R GHVORFDPHQWR GD LPDJHP FRUUHVSRQGHQWH D XP [ TXH p
UHJLVWUDGRQRVLVWHPDGHDTXLVLomRGHGDGRV
$YDULDomRGRkQJXOR pUHODFLRQDGDjPXGDQoDGHtQGLFHGHUHIUDomRQTXHp
FRQVLGHUDGDSURSRUFLRQDOjFRQFHQWUDomRGDVROXomRSROLPpULFDVHJXQGRD(TXDomR


n = Kc (7.14)
RQGH QpDGLIHUHQoDGHtQGLFHGHUHIUDomRHQWUHDVROXomRQDFpOXODGRGHWHFWRUH
DTXHOH GR VROYHQWH SXUR F p D FRQFHQWUDomR GD VROXomR SROLPpULFD H . p XPD
FRQVWDQWHGHSURSRUFLRQDOLGDGHUHODFLRQDGDDRtQGLFHGHUHIUDomRHVSHFtILFR

 &URPDWRJUDILD
)LJXUD(VTXHPDGDOX]UHIUDWDGDDSyVDWUDYHVVDUDFpOXODGRGHWHFWRUGHtQGLFHGHUHIUDomR 

3DUD TXH D VROXomR GH SROtPHUR VHMD GHWHFWDGD p QHFHVViULR TXH R tQGLFH GH
UHIUDomR GR VROYHQWH Q VHMD GLIHUHQWH GR tQGLFH GH UHIUDomR GD VROXomR Q
'HSHQGHQGRGRVYDORUHVGHQHQRVLQDOREVHUYDGRQRUHJLVWUDGRUFRUUHVSRQGHUiD
XPGDTXHOHVLOXVWUDGRVQD)LJXUD

)LJXUD6LQDOHPLWLGRSHORGHWHFWRUGHtQGLFHGHUHIUDomRHPIXQomRGDGLIHUHQoDGHtQGLFHGHUHIUDomR
HQWUHRVROYHQWHHDVROXomR

&DUDFWHUL]DomRGH3ROtPHURV 
2 GHWHFWRU EDVHDGR QR tQGLFH GH UHIUDomR p PXLWR VHQVtYHO j WHPSHUDWXUD H j
WURFDGHVROYHQWHVHSRUWDQWRGHPRUDPDLVDHVWDELOL]DU8PDYH]TXHHVWHWLSRGH
GHWHFWRU WDPEpP p PXLWR VHQVtYHO D YDULDo}HV GH SUHVVmR QR VLVWHPD TXDQGR VH
XWLOL]D PDLV GH XP GHWHFWRU HOH p QRUPDOPHQWH R ~OWLPR DFHVVyULR GR VLVWHPD
FURPDWRJUiILFR

SDetector de ultravioleta
2HVSHFWURIRW{PHWURGHXOWUDYLROHWDYLVtYHOpWDPEpPPXLWRXWLOL]DGRFRPRGHWHFWRU
HPVLVWHPDVGHFURPDWRJUDILDOtTXLGD2SULQFtSLRTXHUHJHHVWHWLSRGHGHWHFWRUpD
OHLGH/DPEHUW%HHUHPTXHDDEVRUYkQFLD$GDOX]XOWUDYLROHWDGHXPDVROXomRD
XP FRPSULPHQWR GH RQGD HVSHFtILFR p SURSRUFLRQDO j FRQFHQWUDomR GD VROXomR
VHJXQGRD(TXDomR

A = .l.c (7.15)

RQGH  p R FRHILFLHQWH GH H[WLQomR RX DEVRUWLYLGDGH PRODU FRQVWDQWH SDUD XP
JUXSR IXQFLRQDO D XP FRPSULPHQWR GH RQGD HVSHFtILFR  O p R FDPLQKR yWLFR RX
HVSHVVXUDGDFpOXODRQGHVHORFDOL]DDVROXomR HFpDFRQFHQWUDomRGDVHVSpFLHVTXH
DEVRUYHP D OX] RX FRQFHQWUDomR GD VROXomR SROLPpULFD  2 WHUPR DEVRUWLYLGDGH
PRODUWHPVLGRPDLVXWLOL]DGRGRTXHRWHUPRFRHILFLHQWHGHH[WLQomR
(PPXLWRVFDVRVRHVSHFWU{PHWURGHXOWUDYLROHWDpSUHIHULGRXPDYH]TXHHVWHp
PHQRV VHQVtYHO D GHWHUPLQDGRV IDWRUHV WDLV FRPR IOXWXDo}HV GH WHPSHUDWXUD
SUHVVmRRXWURFDGHVROYHQWHTXDQGRFRPSDUDGRDRGHWHFWRUEDVHDGRQRtQGLFHGH
UHIUDomR
([LVWHPWUrVWLSRVSULQFLSDLVGHGHWHFWRUHVGH89YLVtYHO
 &RPSULPHQWR GH RQGD VLPSOHV  HVWH GHWHFWRU XWLOL]D ILOWURV H GHWHFWD D
DEVRUYkQFLDGDOX]DXPFRPSULPHQWRGHRQGD
 &RPSULPHQWR GH RQGD YDULiYHO FRQWLQXDPHQWH  HVWH WLSR GH GHWHFWRU XWLOL]D
PRQRFURPDGRUHV H SHUPLWH TXH WRGRV RV FRPSULPHQWRV GH RQGD VHMDP
H[DPLQDGRVHPXPSHUtRGRGHYDUUHGXUDGHDPLQ
 (VSHFWURIRW{PHWUR GH 89YLVtYHO GR WLSR GLRGHDUUD\  QHVWH WLSR GH GHWHFWRU
FRPSULPHQWRV GH RQGD P~OWLSORV LQFLGHP QD DPRVWUD DR PHVPR WHPSR H XP
IRWRGLRGR GLRGHDUUD\  GLVWLQJXH RV GLIHUHQWHV FRPSULPHQWRV GH RQGD
UHFHELGRVGDOX]WUDQVPLWLGD1HVWHFDVRWRGRVRVFRPSULPHQWRVGHRQGDSRGHP
VHUH[DPLQDGRVHPFHUFDGHVHJXQGR
$ )LJXUD  LOXVWUD D GLIHUHQoD GR VLQDO REWLGR TXDQGRVHXVDXPGHWHFWRUGR
WLSR GLRGHDUUD\ RX XP LQVWUXPHQWR FRP XP FRPSULPHQWR GH RQGD IL[R 1R
SULPHLURFDVRREWpPVHXPHVSHFWURFRPSOHWRGDDPRVWUDDFDGDWHPSRGHHOXLomR

 &URPDWRJUDILD
2EYLDPHQWH HVVHV GHWHFWRUHV Vy SRGHP VHU XWLOL]DGRV FRP VXEVWkQFLDV TXH
SRVVXDPJUXSRVFDSD]HVGHDEVRUYHUDOX]QDIDL[DGHFRPSULPHQWRGHRQGDGR89
YLVtYHORXVHMDRVFKDPDGRVJUXSRVFURPyIRURV&RPSRVWRVDURPiWLFRVVmRRVPDLV
VHQVtYHLVDHVWHWLSRGHGHWHFWRU3RURXWURODGRSROtPHURVTXHQmRSRVVXHPJUXSRV
FURPyIRURVWDLVFRPRSROLROHILQDVVmRWUDQVSDUHQWHVQHVWHGHWHFWRU

)LJXUD6LQDOREWLGRGHXPGHWHFWRUGHXOWUDYLROHWDGRWLSR D GLRGHDUUD\H E FRPSULPHQWRGHRQGD


IL[R

SDetector de viscosidade
(VWHWLSRGHGHWHFWRUUHODFLRQDDPXGDQoDGHYLVFRVLGDGHGDVROXomRHPUHODomRjGR
VROYHQWH SXUR 2V SULQFtSLRV EiVLFRV TXH UHJHP HVWDV PXGDQoDV VmR GHVFULWRV QR
&DStWXOR4XDQGRRVROXWRGDVROXomRDVHUDQDOLVDGDSRVVXLEDL[RSHVRPROHFXODU
DGLIHUHQoDGHYLVFRVLGDGHHQWUHRVROYHQWHSXURHDVROXomRpPXLWRSHTXHQDSDUD
VHU GHWHFWDGD SRU HVWH WLSR GH WpFQLFD 'HVWD IRUPD RV GHWHFWRUHV EDVHDGRV HP
PHGLGDV GH YLVFRVLGDGH GH VROXomR Vy VmR XWLOL]DGRV SDUD DQiOLVH GH VROXo}HV
SROLPpULFDV
$ HTXDomR GH 3RLVHXLOOH (TXDomR   FRQVWLWXL D EDVH SDUD DV PHGLGDV GH
YLVFRVLGDGHGDVROXomRHPFURPDWRJUDILDGHH[FOXVmRSRUWDPDQKR YHUFDStWXOR 

&DUDFWHUL]DomRGH3ROtPHURV 
.p.r 4
= (7.16)
8.L.Q
RQGH SpDGLIHUHQoDGHSUHVVmRDRORQJRGRFDSLODUGRYLVFRVtPHWURUpRUDLRGR
FDSLODU/pRFRPSULPHQWRGRFDSLODUH4pDYHORFLGDGHGHIOX[RGROtTXLGRPHGLGD
HPYROXPHSRUXQLGDGHGHWHPSR
$YLVFRVLGDGHGDVROXomRHOXHQWHGRFURPDWyJUDIRGHH[FOXVmRSRUWDPDQKRSRGH
VHUGHWHUPLQDGDGHGXDVIRUPDV
SPHGLGDGRWHPSRQHFHVViULRSDUDXPGHWHUPLQDGRYROXPHGHHOXHQWHDWUDYHVVDU
RFDSLODUGRYLVFRVtPHWUR
SPHGLGDGDTXHGDGHSUHVVmRUHVXOWDQWHGDSDVVDJHPGRHOXHQWHQRFDSLODU
(PERUDRSULPHLURPpWRGRVHMDSRVVtYHOSDUDPHGLGDVGHYLVFRVLGDGHRIIOLQH
TXDQGRRYLVFRVtPHWURpDFRSODGRDXPVLVWHPDFURPDWRJUiILFR PHGLGDVRQOLQH 
D GHWHUPLQDomR GD TXHGD GH SUHVVmR IRUQHFH XPD PHGLGD FRQWtQXD GD YLVFRVLGDGH
GDVROXomR
1RV YLVFRVtPHWURV RQOLQH XWLOL]DGRV HP FURPDWRJUDILD OtTXLGD D TXHGD GH
SUHVVmR GD DPRVWUD HOXHQWH SL p PHGLGD QR FDSLODU H FRPSDUDGD j TXHGD GH
SUHVVmRSURYRFDGDSHORVROYHQWHSXUR S$WpFQLFDpEDVHDGDQDGHWHUPLQDomRGD
YLVFRVLGDGHLQWUtQVHFDLQVWDQWkQHD>@LXWLOL]DQGRD(TXDomR

1 p 1 p p0
[ ]i = 1
log i log i = i (7.17)
ci 0 ci p0 ci p0
RQGHFLpDFRQFHQWUDomRGDVROXomR
3DUD D GHWHUPLQDomR GD YLVFRVLGDGH LQWUtQVHFD GD VROXomR D FDGD WHPSR GH
HOXLomRRGHWHFWRUEDVHDGRQDPHGLGDGDYLVFRVLGDGHpXWLOL]DGRMXQWRDXPRXWUR
GHWHFWRU EDVHDGR HP PXGDQoD GH DOJXPD SURSULHGDGH FRP D FRQFHQWUDomR
QRUPDOPHQWHRGHWHFWRUGHtQGLFHGHUHIUDomR  YHUFDStWXOR 
2GHWHFWRUYLVFRVLPpWULFRpXWLOL]DGRSULQFLSDOPHQWHSDUDGHWHUPLQDomRGHSHVR
PROHFXODU GH SROtPHURV $ WpFQLFD FURPDWRJUiILFD TXH VHSDUD RV FRPSRQHQWHV GH
XPDVROXomRSHORWDPDQKRPROHFXODUpDFURPDWRJUDILDGHH[FOXVmRSRUWDPDQKRD
VHUGLVFXWLGDQRLWHP2SHVRPROHFXODULQVWDQWkQHR0LGRSROtPHURGLVVROYLGR
QDVROXomRHOXHQWHSRGHVHUGHWHUPLQDGRSRUPHLRGDHTXDomRGH0DUN+RXZLQN
GLVFXWLGDQRFDStWXORHDSUHVHQWDGDDVHJXLU

[ i ] = K.M ia (7.18)

 &URPDWRJUDILD
RQGHRVSDUkPHWURV.HDSRGHPVHUFRQVLGHUDGRVFRQVWDQWHVSDUDXPGHWHUPLQDGR
VROYHQWHHWHPSHUDWXUDH0LpRSHVRPROHFXODUYLVFRVLPpWULFR6HDVFRQVWDQWHVGD
HTXDomR GH 0DUN+RXZLQN QmR VmR FRQKHFLGDV R FRQFHLWR GH FDOLEUDomR XQLYHUVDO
GHYHVHUXWLOL]DGR(VWHFRQFHLWRVHUiGHVFULWRQDVHVVmR

SDetector de espalhamento de luz


2 GHWHFWRU GH HVSDOKDPHQWR GH OX] WDPEpP p XWLOL]DGR SDUD PHGLGDV GH SHVR
PROHFXODUGHSROtPHURVSRUFURPDWRJUDILDGHH[FOXVmRSRUWDPDQKR2SULQFtSLRTXH
UHODFLRQDDLQWHQVLGDGHGDOX]HVSDOKDGDFRPRSHVRPROHFXODUGHXPSROtPHURIRL
GLVFXWLGRQRFDStWXORHXWLOL]DD(TXDomR

Kc 1
= + 2 A2 c + 3 A3 c 2 + ...... (7.19)
R M
RQGH5pDGLIHUHQoDHQWUHDVUD]}HVGH5D\OHLJKGDVROXomRHGRVROYHQWHSXUR$
H $ VmR FRQKHFLGRV UHVSHFWLYDPHQWH FRPR VHJXQGR FRHILFLHQWH YLULDO H WHUFHLUR
FRHILFLHQWHYLULDO M pRSHVRPROHFXODUSRQGHUDOPpGLRH.pXPSDUkPHWURTXH
GHSHQGH GD YDULDomR GR tQGLFH GH UHIUDomR FRP D FRQFHQWUDomR GD VROXomR YHU
FDStWXOR 
2VGHWHFWRUHVEDVHDGRVQDWpFQLFDGHHVSDOKDPHQWRGHOX]XWLOL]DPIRQWHVGHOX]
ODVHU VHQGR D OX] HVSDOKDGD PHGLGD D EDL[R kQJXOR FHUFD GH R  8WLOL]DQGRVH
PHGLGDVDEDL[RkQJXORWRUQDVHGHVQHFHVViULDDH[WUDSRODomRDkQJXOR]HURSDUDD
GHWHUPLQDomRGHUDLRGHJLUDomR
eLPSRUWDQWHUHVVDOWDUTXHHVWDWpFQLFDpPXLWRVHQVtYHOjSUHVHQoDGHTXDOTXHU
LPSXUH]D(VWHGHWHFWRUpSRUWDQWRFUtWLFRTXDQGRVHXWLOL]DPFROXQDVGHVtOLFDQD
FURPDWRJUDILD XPD YH] TXH HVWDV VHPSUH OLEHUDP SHTXHQDV SDUWtFXODV TXH YmR
LQIOXHQFLDUVHQVLYHOPHQWHRVUHVXOWDGRVGHSHVRPROHFXODUREWLGRV
3DUDDWpFQLFDGHHVSDOKDPHQWRGHOX]DFRSODGDDXPFURPDWyJUDIROtTXLGRSDUD
PHGLGDVGHSHVRPROHFXODU FURPDWRJUDILDGHH[FOXVmRSRUWDPDQKR DVVXPHVHTXH
RLQFUHPHQWRGRtQGLFHGHUHIUDomRVHMDFRQVWDQWHSDUDFDGDYROXPHHOXtGR&RPRMi
GLVFXWLGR QR &DStWXOR  D UD]mR GH 5D\OHLJK GHSHQGH GD YDULDomR GR tQGLFH GH
UHIUDomRFRPDFRQFHQWUDomRGDVROXomR$XWLOL]DomRGRGHWHFWRUGHHVSDOKDPHQWR
GH OX] QmR p SRUWDQWR UHFRPHQGiYHO SDUD FDUDFWHUL]DomR GH FRSROtPHURV SRUTXH
YDULDo}HVQDFRPSRVLomRGRFRSROtPHURFDXVDPYDULDo}HVQRLQFUHPHQWRGRtQGLFH
GHUHIUDomR

&DUDFWHUL]DomRGH3ROtPHURV 
7.4.2 Cromatografia por adsoro
7.4.2.1 Mecanismo da cromatografia lquido - slido (adsoro)
$ FURPDWRJUDILD SRU DGVRUomR XWLOL]D D FDSDFLGDGH GH XPD IDVH HVWDFLRQiULD HP
DGVRUYHU GH PRGR PDLV RX PHQRV HIHWLYR RV FRPSRQHQWHV LQGLYLGXDLV GH XPD
PLVWXUD$WpFQLFDGHSHQGHGDVLQWHUDo}HVHVSHFtILFDVGRVROXWRFRPDVXSHUItFLHGH
XPDGVRUYHQWH IDVHHVWDFLRQiULD ILQDPHQWHGLYLGLGR
&RQVLGHUHPRV XP FDVR EHP VLPSOHV XPD VXEVWkQFLD RX DPRVWUD 6 HP XP
HOXHQWH ( &RQVLGHUHPRV DLQGD TXH D DGVRUomR H GHVVRUomR VmR SURFHVVRV
UHYHUVtYHLV$VPROpFXODVGRVROXWRHGDIDVHPyYHOFRPSHWHPHQWUHVLSHORFHQWUR
DWLYR GR DGVRUYHQWH IDVH HVWDFLRQiULD  RX VHMD RV FHQWURV DWLYRV QD VXSHUItFLH GD
IDVH HVWDFLRQiULD VmR RFXSDGRV RUD SHOD VXEVWkQFLD D VHU DQDOLVDGD RUD SHODV
PROpFXODV GR HOXHQWH (VWD FRPSHWLomR SRGH VHU UHSUHVHQWDGD SHOD VHJXLQWH
HTXDomR

Sm + nEads Sads + nEm (7.20)

RQGH6PH6DGVUHSUHVHQWDPDPROpFXODGRVROXWRQDIDVHPyYHOHQDIDVHHVWDFLRQiULD
UHVSHFWLYDPHQWH (P H (DGV UHSUHVHQWDP D PROpFXOD GR VROYHQWH QD IDVH PyYHO H QD
IDVHHVWDFLRQiULDUHVSHFWLYDPHQWH
4XDQGR D PROpFXOD GR VROXWR 6 ORFDOL]DGD QD IDVH PyYHO p DGVRUYLGD SHOD IDVH
HVWDFLRQiULD HOD GHVORFD Q PROpFXODV GR HOXHQWH LQLFLDOPHQWH DGVRUYLGDV QD IDVH
HVWDFLRQiULD2IDWRUQLQGLFDRQ~PHURGHPROpFXODVGDIDVHPyYHOTXHSUHFLVDVHU
GHVORFDGR GD IDVH HVWDFLRQiULD SDUD DFRPRGDU D PROpFXOD GR VROXWR $ SDUWLU GD
(TXDomRSRGHPRVHVFUHYHUDVHJXLQWHHTXDomRSDUDDFRQVWDQWHGHHTXLOtEULR

K=
(S ads )(Em )
n

(S m )(Eads )n   

(VWD HTXDomR PRVWUD TXH D LQWHUDomR DGVRUYHQWH  VROXWR p R SDUkPHWUR PDLV


LPSRUWDQWH TXH JRYHUQD D VHSDUDomR HP XPD FURPDWRJUDILD SRU DGVRUomR 6H D
DGVRUomR GD IDVH PyYHO HOXHQWH  DXPHQWD D DGVRUomR GR VROXWR GLPLQXL H D
DPRVWUDGRVROXWRHOXLUiPDLVUiSLGR

 &URPDWRJUDILD
7.4.2.2 Tipos de adsorventes e interaes com solutos
2V GRLV DGVRUYHQWHV PDLV SRSXODUHV QD FURPDWRJUDILD GR WLSR VyOLGR  OtTXLGR VmR
VtOLFD 6L2 [ H DOXPLQD $O2 [ $ VtOLFD p FRQVLGHUDGD PDLV YHUViWLO 7DQWR D VtOLFD
FRPR D DOXPLQD SRVVXHP JUXSRV DWLYRV QD VXSHUItFLH TXH GHWHUPLQDP DV
FDUDFWHUtVWLFDVGDDGVRUomR([HPSORV

 &RQVLGHUHPRVXPDPLVWXUDGHEHQ]HQRDFHWRIHQRQDHiOFRROEHQ]tOLFR
1HVWHFDVRpIiFLOSUHYHUDRUGHPGHUHWHQomRGHVWHVFRPSRQHQWHV&RPRDIDVH
HVWDFLRQiULD p SRODU RV FRQVWLWXLQWHV PDLV SRODUHV LUmR LQWHUDJLU PDLV IRUWHPHQWH
FRP D IDVH HVWDFLRQiULD H SRUWDQWR ILFDUmR UHWLGRV SRU PDLV WHPSR QD FROXQD 'H
DFRUGRFRPDSRODULGDGHGRVFRQVWLWXLQWHVGDPLVWXUDDRUGHPGHHOXLomRVHUi
1) benzeno 2) acetofenona 3) lcool benzlico
24XDGURDSUHVHQWDDOJXPDVFODVVHVGHVXEVWkQFLDVHPRUGHPFUHVFHQWHGH
SRODULGDGH

 &RPSRQHQWHV LVRPpULFRV SRGHP VHU VHSDUDGRV GHYLGR DR DUUDQMR HVSDFLDO GRV
JUXSRVKLGUR[LODQDVXSHUItFLHGDVtOLFD3RUH[HPSORDKLGURTXLQRQDHRFDWHFRO
LQWHUDJHP GH PDQHLUD GLIHUHQWH FRP D VXSHUItFLH GD VtOLFD FRPR PRVWUD R
HVTXHPDGD)LJXUD2LV{PHURSDUD GHQRPLQDGRKLGURTXLQRQD pFDSD]GH
LQWHUDJLUFRPGRLVFHQWURVDWLYRVVLPXOWDQHDPHQWH2LV{PHURRUWR GHQRPLQDGR
FDWHFRO  Vy LQWHUDJH FRP XP FHQWUR DWLYR SRU FDXVD GR DUUDQMR GH VHXV JUXSRV
IXQFLRQDLV6HSDUDomRGHLV{PHURV

 $VHSDUDomRGHRUWRPHWDHSDUDQLWURDQLOLQDVpHVTXHPDWL]DGDQD)LJXUD
2EVHUYDVHTXHRLV{PHURSDUDpHOXtGRSRU~OWLPRGHYLGRjVIRUWHVLQWHUDo}HV
FRP D VXSHUItFLH GD IDVH HVWDFLRQiULD SRODU 2 LV{PHUR RUWR p HOXtGR SULPHLUR
SRUTXH DV LQWHUDo}HV VmR PDLV IUDFDV 1HVWH FDVR H[LVWH D SRVVLELOLGDGH GH
IRUPDomR GH SRQWHV GH KLGURJrQLR LQWUDPROHFXODU QR FRPSRVWR GLPLQXLQGR D
FKDQFHGHLQWHUDomRFRPRPDWHULDODGVRUYHQWH2LV{PHURPHWDSRVVXLPHQRU

&DUDFWHUL]DomRGH3ROtPHURV 
LQWHUDomR GR TXH R LV{PHUR SDUD GHYLGR DR DUUDQMR PROHFXODU QD VXSHUItFLH 2
WHPSRGHHOXLomRGHVWHLV{PHURpHQWUHWDQWRPDLRUGRTXHRGRLV{PHURRUWR
SRUTXHQmRH[LVWHSRVVLELOLGDGHGHLQWHUDomRLQWUDPROHFXODU
4XDGUR&ODVVHGHVXEVWkQFLDHPRUGHPFUHVFHQWHGHSRODULGDGH

Fluorocarbonetos <
hidrocarbonetos saturados <
olefinas <
hidrocarbonetos aromticos <
compostos halogenados <
ter <
compostos nitrados <
steres, cetonas, aldeidos <
lcoois, aminas <
amidas <
cidos carboxlicos

)LJXUD,QWHUDo}HVHQWUHDVXSHUItFLHGDVtOLFDHGLKLGUR[LEHQ]HQRVLVRPpULFRV

 &URPDWRJUDILD
)LJXUD&URPDWRJUDPDWtSLFRGHVHSDUDomRGHLV{PHURVGDQLWURDQLOLQD

7.4.2.3 Seleo de solventes como fase mvel


$DGVRUomRGHXPVROXWRQDIDVHHVWDFLRQiULDSRGHVHUWmRIRUWHGHSHQGHQGRGDVXD
SRODULGDGHTXHRWHPSRGHUHWHQomRSRGHVHWRUQDUPXLWRORQJR(PDOJXQVFDVRV
XPDDGVRUomRLUUHYHUVtYHOSRGHRFRUUHU3DUDUHGX]LURVHIHLWRVGDVLQWHUDo}HVPXLWR
IRUWHV D DWLYLGDGH GR DGVRUYHQWH IDVH HVWDFLRQiULD  SRGH VHU FRQWURODGD RX
PRGLILFDGDXWLOL]DQGRVHXPYROXPHIL[RGHiJXDRXiOFRRO
eLPSRUWDQWHOHPEUDUTXHRVROYHQWHHRVROXWRHVWmRHPFRQVWDQWHFRPSHWLomR
SHORV VtWLRV DWLYRV QD VXSHUItFLH GR DGVRUYHQWH /RJR TXDQWR PDLV SRODU IRU D IDVH
PyYHO PDLRU VHUi D VXD LQWHUDomR FRP D IDVH HVWDFLRQiULD H PDLV UiSLGR R VROXWR
VHUi HOXLGR 'HVWD IRUPD R IDWRU GHWHUPLQDQWH QD UHWHQomR RX VHSDUDomR HP XPD
FURPDWRJUDILD VyOLGROtTXLGR p D SRODULGDGH UHODWLYD GD IDVH PyYHO H GR VROXWR 1R
SURFHVVRFURPDWRJUiILFRXPVROYHQWHPDLVSRODUGHVORFDUiRVROYHQWHPHQRVSRODU
GD VXSHUItFLH GR DGVRUYHQWH (VWD HVFDOD p GHQRPLQDGD VpULH HOXRWUySLFD TXH IRL
GHVHQYROYLGD SDUD DOXPLQD FRPR DSUHVHQWDGD QD 7DEHOD  (VWD WDEHOD VHUYH
VRPHQWHFRPRXPJXLDXPDYH]TXHDSRODULGDGHUHODWLYDSRGHPXGDUGHSHQGHQGR
GR WLSR GH DPRVWUD H GH DGVRUYHQWH 2 WHUPR R FRQKHFLGR FRPR SDUkPHWUR GH
IRUoDGRVROYHQWHpXPDUHSUHVHQWDomRTXDQWLWDWLYDGDIRUoDGRVROYHQWH
3DUDDREWHQomRGHXPDIDVHPyYHOFRPIRUoDLQWHUPHGLiULDHQWUHRVYDORUHVGH
DSUHVHQWDGRVQD7DEHODFRVWXPDVHXWLOL]DUPLVWXUDVGHVROYHQWHV
R

&DUDFWHUL]DomRGH3ROtPHURV 
7DEHOD6pULHHOXRWUySLFDSDUDDOXPLQD

6ROYHQWH R 
QSHQWDQR 
LVRFWDQR 
FLFORKH[DQR 
WHWUDFORUHWRGHFDUERQR 
[LOHQR 
WROXHQR 
EHQ]HQR 
pWHUHWtOLFR 
FORURIyUPLR 
WHWUDKLGURIXUDQR 
DFHWRQD 
DFHWRQLWULOD 
LSURSDQRO 
PHWDQRO 

7.4.2.4 A utilizao da cromatografia por adsoro em polmeros


(P PXLWRV DVSHFWRV D DGVRUomR GH XPD PDFURPROpFXOD SRVVXL FRPSRUWDPHQWR
VHPHOKDQWH jTXHOH DSUHVHQWDGR SRU PROpFXODV SHTXHQDV $OJXPDV GLIHUHQoDV
HQWUHWDQWRGHYHPVHUHQIDWL]DGDV3RUH[HPSORDTXDQWLGDGHDGVRUYLGDXVXDOPHQWH
DXPHQWDFRPRSHVRPROHFXODUGRVROXWRRXVHMDDDGVRUomRFUHVFHFRPRWDPDQKR
PROHFXODU4XDQWRPDLVSREUHIRURVROYHQWHFRQVWLWXLQWHGDIDVHPyYHOPDLRUVHUi
RHIHLWRGRSHVRPROHFXODUQRWHPSRGHHOXLomR
2XWURIDWRULQWHUHVVDQWHpDVXSHUItFLHGRDGVRUYHQWH$PDLRULDGRVDGVRUYHQWHV
SRVVXL XPD iUHD VXSHUILFLDO HVSHFtILFD H[WUHPDPHQWH JUDQGH GHYLGR j VXD DOWD
SRURVLGDGH$iUHDVXSHUILFLDOLQWHUQDGRVSRURVSRGHVHUFRPSOHWDPHQWHXWLOL]DGD
VHRVSRURVVmRJUDQGHVTXDQGRFRPSDUDGRVDRWDPDQKRGDVPROpFXODVDGVRUYLGDV
(QWUHWDQWRPROpFXODVGHSROtPHURVFRPDOWRSHVRPROHFXODUSRGHPDSUHVHQWDUXP
WDPDQKREHPPDLRUGRTXHRVSRURVGDIDVHHVWDFLRQiULD&RQVHTHQWHPHQWHHVWD
PDFURPROpFXOD QmR SRGHUi LQWHUDJLU WRWDOPHQWH FRP D VXSHUItFLH WRWDO GR
DGVRUYHQWHHHOXLUiDXPWHPSRPHQRU
$)LJXUDDSUHVHQWDXPDUHSUHVHQWDomRHVTXHPiWLFDGDGHSHQGrQFLDHQWUHD
TXDQWLGDGHGHSROtPHURDGVRUYLGRHPXPDGHWHUPLQDGDIDVHHVWDFLRQiULDHRVHX
SHVRPROHFXODU$FXUYDDSUHVHQWDXPPi[LPRDXPGHWHUPLQDGRSHVRPROHFXODU
3DUD SHVRV PROHFXODUHV PHQRUHV GR TXH DTXHOH UHSUHVHQWDGR QHVWH SRQWR D
TXDQWLGDGH GH SROtPHUR DGVRUYLGR FUHVFH FRP R SHVR PROHFXODU GHYLGR j PDLRU
SRVVLELOLGDGHGHLQWHUDomRHQWUHSROtPHURHDGVRUYHQWH$SDUWLUGRSRQWRPi[LPRD

 &URPDWRJUDILD
PDFURPROpFXODWRUQDVHPXLWRJUDQGHSDUDLQWHUDJLUFRPWRGRVRVFHQWURVDWLYRVGD
IDVH HVWDFLRQiULD ORFDOL]DGRV LQFOXVLYH GHQWUR GRV SRURV SHTXHQRV 2V SRQWRV GH
LQWHUDomRGLPLQXHPHDTXDQWLGDGHGHSROtPHURDGVRUYLGRWDPEpPGLPLQXL

)LJXUD5HODomRHQWUHDTXDQWLGDGHGHSROtPHURDGVRUYLGRHPXPVXSRUWHSRODUHSRURVRHRSHVR
PROHFXODUGRSROtPHUR

7.4.3 Cromatografia de partio Limite de excluso


2 SULQFtSLR GD VHSDUDomR SRU FURPDWRJUDILD GH SDUWLomR WDPEpP FKDPDGD
FURPDWRJUDILD OtTXLGR  OtTXLGR p R PHVPR TXH DTXHOH HQYROYLGR HP H[WUDomR GH
XPDVXEVWkQFLDXWLOL]DQGRVHGRLVOtTXLGRVLPLVFtYHLVHPXPIXQLOGHVHSDUDomR
(PVXDIRUPDPDLVVLPSOHVDFURPDWRJUDILDGHSDUWLomRpDOFDQoDGDIL[DQGRXP
OtTXLGR LPLVFtYHO HP XP VXSRUWH DWUDYpV GR TXDO D IDVH PyYHO p HOXtGD $ IDVH
HVWDFLRQiULDpSRUWDQWRFRQVWLWXtGDGROtTXLGRTXHHVWiDGHULGRDXPVXSRUWHVyOLGR
TXDOTXHU 2V GRLV OtTXLGRV HVWmR HP FRQWDWR tQWLPR H SHUPLWH D RFRUUrQFLD GH
P~OWLSODVH[WUDo}HVGXUDQWHDHOXLomR
$ FURPDWRJUDILD SRU SDUWLomR SRGH VHU GLYLGLGD HP GRLV JUDQGHV JUXSRV
FURPDWRJUDILDOtTXLGROtTXLGRHFURPDWRJUDILDSRUIDVHOLJDGD ERXQGHGSKDVH 
1D FURPDWRJUDILD OtTXLGR  OtTXLGR DV FROXQDV VmR SUHSDUDGDV UHFREULQGR XP
VXSRUWH FRP XPD IDVH HVWDFLRQiULD GD PHVPD IRUPD FRPR p UHFREHUWR R VXSRUWH
SDUDXPDFURPDWRJUDILDHPIDVHJDVRVD2XVHMDDIDVHHVWDFLRQiULDOtTXLGDQmRHVWi
TXLPLFDPHQWH OLJDGD DR VXSRUWH 8P GRV UHTXLVLWRV SDUD XP ERP GHVHPSHQKR
QHVWH WLSR GH VHSDUDomR p D FRPSOHWD LPLVFLELOLGDGH HQWUH D IDVH PyYHO H D IDVH
HVWDFLRQiULDDPEDVOtTXLGDV1DSUiWLFDIDVHVHVWDFLRQiULDVWtSLFDVFRPR&DUERZD[

&DUDFWHUL]DomRGH3ROtPHURV 
DSUHVHQWDPXPDSHTXHQDVROXELOLGDGHHPWRGDVDVIDVHVPyYHLVXWLOL]DGDV&RPR
WHPSRGHXVRGHVWDVFROXQDVDIDVHHVWDFLRQiULDYDLVHQGROHQWDPHQWHUHPRYLGDGR
VXSRUWHSHODIDVHPyYHO(VWHIHQ{PHQRFDXVDXPDGHWHULRUDomRGRGHVHPSHQKRGD
FROXQDDRORQJRGRXVRRXVHMDGLPLQXLDYLGD~WLOGDFROXQD
$ FURPDWRJUDILD GR WLSR ERXQGHGSKDVH WHP VH WRUQDGR D PDLV SRSXODU HP
+3/& (VWD WpFQLFD HOLPLQD RV SUREOHPDV HQFRQWUDGRV QD FURPDWRJUDILD OtTXLGR 
OtTXLGR FRQYHQFLRQDO SRUTXH D IDVH HVWDFLRQiULD HVWi TXLPLFDPHQWH OLJDGD DR
VXSRUWH

7.4.3.1. Mecanismo da separao em uma cromatografia de partio


4XDQGRXPVROXWRpDGLFLRQDGRDXPVLVWHPDFRQWHQGRGRLVOtTXLGRVLPLVFtYHLVHR
VLVWHPD FRPR XP WRGR p GHL[DGR DWp TXH VH DWLQMD R HTXLOtEULR R VROXWR LUi VH
GLVWULEXLUHQWUHDVGXDVIDVHVGHDFRUGRFRPD(TXDomR

Cs
K = (7.22)
Cm
RQGH . p R FRHILFLHQWH GH GLVWULEXLomR H &V H &P VmR DV FRQFHQWUDo}HV GR VROXWR QD
IDVHHVWDFLRQiULDHQDIDVHPyYHOUHVSHFWLYDPHQWH
2 IDWRU FDSDFLGDGH p UHODFLRQDGR DR FRHILFLHQWH GH GLVWULEXLomR D SDUWLU GD
(TXDomR

gm
K '= (7.23)
gs
RQGH
gm = gramas do soluto na fase mvel = (Cm) (Vm) (7.24)

gs = gramas de soluto na fase estacionria = (Cs) (Vs) (7.25)


&RPELQDQGRD(TXDomRFRPDV(TXDo}HVHREWHPRV

Cs g s Vm Vm
K= = x = K' (7.26)
Cm g m Vs Vs
RX

 &URPDWRJUDILD
Vs
K '= K (7.27)
Vm
$ FDSDFLGDGH GH UHWHQomR GR VROXWR QD IDVH HVWDFLRQiULD p FRQWURODGD SHOR
FRHILFLHQWH GH GLVWULEXLomR H SHOD UD]mR HQWUH RV YROXPHV GH VROXomR GR VROXWR QD
IDVH HVWDFLRQiULD H QD IDVH PyYHO 8P VROXWR PXLWR VRO~YHO QD IDVH HVWDFLRQiULD
ILFDUiUHWLGRSRUPDLVWHPSR

7.4.3.2 Natureza dos suportes com a superfcie quimicamente modificada


('bonded phases")
$ IDVH HVWDFLRQiULD PDLV XWLOL]DGD DWXDOPHQWH p DTXHOD TXLPLFDPHQWH OLJDGD DR
VXSRUWH SDUD HYLWDU R DUUDVWH GD IDVH HVWDFLRQiULD FRP R WHPSR ([LVWHP YiULRV
PpWRGRV SDUD OLJDU TXLPLFDPHQWH D IDVH HVWDFLRQiULD DR VXSRUWH 7RGRV HOHV
HQYROYHPXPDUHDomRFRPRJUXSRUHDWLYRVLODQRO 6L2+ QDVXSHUItFLHGDVtOLFD
2 SULPHLUR PpWRGR HQYROYH D UHDomR GH HWHULILFDomR HQWUH RV JUXSRV VLODQRO GR
VXSRUWHHRVJUXSRVKLGUR[LODVLWXDGRVQDH[WUHPLGDGHGHXPDFDGHLDGHXPiOFRRO
$V OLJDo}HV pWHU VmR IDFLOPHQWH KLGUROLViYHLV H VmR WDPEpP WHUPLFDPHQWH
LQVWiYHLV 3RUWDQWR HVWH WLSR GH IDVH HVWDFLRQiULD QmR p DGHTXDGR SDUD PXLWDV
DSOLFDo}HV

HOR
Si OH Si OR

)DVHV TXLPLFDPHQWH OLJDGDV HQYROYHQGR UHDo}HV GH VLODQL]DomR WrP VH WRUQDGR
PDLV SRSXODUHV SRUTXH D OLJDomR VLOR[DQD 6L26L  p PDLV HVWiYHO HP VROYHQWHV
FRPXQVGHFURPDWRJUDILD$OLJDomR6L&OTXHQmRUHDJLXSRGHVHUKLGUROLVDGDD6L2+
HHPVHJXLGDUHDJLGDFRP &+ 6L&O
(VWH WLSR GH HPSDFRWDPHQWR p JHUDOPHQWH HVWiYHO HP S+ QD IDL[D GH  D  H
WHPSHUDWXUDVDWp&
R
R2SiCl2
Si OH Si O-SiCl + HCl
R
8P WHUFHLUR WLSR GH UHDomR HQYROYH D XWLOL]DomR GH FORUHWR GH WLRQLOD 2 FORUR
OLJDGRDRiWRPRGHVLOtFLRpHQWmRVXEVWLWXtGRSRUXPJUXSR5 DOTXLOD TXDOTXHUD

&DUDFWHUL]DomRGH3ROtPHURV 
SDUWLUGHXPDUHDomRGHVXEVWLWXLomRQXFOHRItOLFDHQYROYHQGRUHDJHQWHGH*ULJQDUG
RXXPDDPLQDVXEVWLWXtGD

RMgBr Si R
SOCl2
Si OH Si Cl
RNH2

Si NHR

8P JUDQGH Q~PHUR GH JUXSRV IXQFLRQDLV SRGH HP SULQFtSLR VHU OLJDGR DRV
JUXSRVVLODQROQDVXSHUItFLHGRVXSRUWH1DSUiWLFDRVPDLVFRPXQVVmRRVJUXSRV
RFWLOD RFWDGHFLOD IHQLOD DOTXLODPLQD H DOTXLOQLWULOD (VWHV WLSRV GH IDVH DWLYD
FRQIHUHPXPDDPSODIDL[DGHSRODULGDGHjIDVHHVWDFLRQiULD24XDGURDSUHVHQWD
XPD OLVWD GDV SULQFLSDLV IDVHV HVWDFLRQiULDV TXLPLFDPHQWH OLJDGDV DR VXSRUWH GH
VtOLFDHPRUGHPGHFUHVFHQWHGHSRODULGDGH
4XDQGRDIDVHHVWDFLRQiULDpPDLVSRODUGRTXHDIDVHPyYHODWpFQLFDpFKDPDGD
GH FURPDWRJUDILD FRP IDVH OLJDGD QRUPDO 4XDQGR FRPSRVWRV DSRODUHV SUHFLVDP VHU
VHSDUDGRVQRUPDOPHQWHXWLOL]DVHXPDIDVHHVWDFLRQiULDPHQRVSRODUGRTXHDIDVH
PyYHO1HVWHFDVRDWpFQLFDpFKDPDGDFURPDWRJUDILDFRPIDVHOLJDGDUHYHUVD$PEDV
DVWpFQLFDVVHSDUDPRVFRPSRQHQWHVSRUSDUWLomR
$ VHJXLU VHUmR DSUHVHQWDGRV DOJXQV H[HPSORV GH VHSDUDomR GH VXEVWkQFLDV
XWLOL]DQGRVHDFURPDWRJUDILDGHSDUWLomR
 )WDODWRV VmR PXLWR XWLOL]DGRV FRPR DJHQWHV SODVWLILFDQWHV SDUD SROL FORUHWR GH
YLQLOD  39&  &RP R WHPSR HQWUHWDQWR HOHV SRGHP VHU UHPRYLGRV GR PDWHULDO
SOiVWLFR H FRQWDPLQDU R FRQWH~GR GR UHFLSLHQWH e LPSRUWDQWH SRUWDQWR D
GHWHFomR GHVWHV PDWHULDLV HP OtTXLGRV TXH HVWHMDP HP FRQWDWR FRP R 39&
SODVWLILFDGR $ )LJXUD  LOXVWUD D VHSDUDomR GH DOJXQV IWDODWRV QRUPDOPHQWH
HQFRQWUDGRVHPDPRVWUDVGH39&$VHSDUDomRIRLIHLWDXWLOL]DQGRVHFROXQDFRP
IDVH HVWDFLRQiULD OLJDGD j EDVH GH QLWULOD WHQGR FRPR HOXHQWH IDVH PyYHO 
KHSWDQR &RPR D FROXQD SRVVXL QDWXUH]D SRODU R FRPSRQHQWH PDLV SRODU
DSUHVHQWDUi PDLRU WHPSR GH UHWHQomR )WDODWR GH GLPHWLOD ILFD UHWLGR QD FROXQD
SRU PDLV WHPSR SRUTXH RV JUXSRV DOTXLOD VmR PHQRUHV H D PROpFXOD WRUQDVH
PDLVSRODU



 &URPDWRJUDILD
4XDGUR/LVWDGDVSULQFLSDLVIDVHVHVWDFLRQiULDVTXLPLFDPHQWHOLJDGDVDRVXSRUWHGHVLOLFD 

*UXSRDWLYR (VWUXWXUD
OH OH
JOLFRO
Si (CH2)3-O-CH2-CH-CH2

DPLQR Si (CH2)3 NH2

QLWUR Si (CH2)3 NO
2

R[DQLWULOD Si (CH2)3-OCH2CH2 CN

QLWULOD Si (CH2)3 CN

NH2
DPLQRDULOD

NO2
QLWURDULOD

GLPHWLODPLQD Si (CH2)3 N(CH3)2

DOLOIHQLOD Si R CH2 CH=CH2

IHQLOD Si

QKH[LOD Si (CH 2)5CH 3

QRFWLOD Si (CH2)7CH3

QRFWDGHFLOD Si (CH 2)17CH 3

&DUDFWHUL]DomRGH3ROtPHURV 
 2OHILQDVVmRFRPSRVWRVDSRODUHVHSRUWDQWRSDUDDVXDVHSDUDomRpLPSRUWDQWH
DXWLOL]DomRGHIDVHHVWDFLRQiULDDSRODU$)LJXUDLOXVWUDDVHSDUDomRGHXPD
VpULH GH PRQRROHILQDV XWLOL]DQGRVH FRPR IDVH HVWDFLRQiULD R RFWDGHFLOVLODQR
OLJDGR DR VXSRUWH GH VtOLFD H FRPR IDVH PyYHO D DFHWRQLWULOD 1RWDVH TXH DV
ROHILQDVFRPSHVRVPROHFXODUHVPDLRUHVHOXLUmRDWHPSRVPDLRUHV

)LJXUD6HSDUDomRGHSODVWLILFDQWHVGRWLSRIWDODWRVSRUFURPDWRJUDILDOtTXLGDGHSDUWLomR 

)LJXUD6HSDUDomRGHPRQRROHILQDVSRUFURPDWRJUDILDOtTXLGDGHSDUWLomR

 &URPDWRJUDILD
7.4.4 Cromatografia de excluso por tamanho
$FURPDWRJUDILDGHH[FOXVmRSRUWDPDQKR 6(& pXPGRVPpWRGRVPDLVSRSXODUHV
GHVHSDUDomRHDQiOLVHGHPDWHULDLVSROLPpULFRV2VPpWRGRVGHVFULWRVQRVFDStWXORV
DQWHULRUHV IRUQHFHP EDVLFDPHQWH RV YDORUHV GH SHVR PROHFXODU QXPpULFR PpGLR
SRQGHUDOPpGLRRXYLVFRVLPpWULFRPpGLRGHSHQGHQGRGRPpWRGR1DFURPDWRJUDILD
GHH[FOXVmRSRUWDPDQKRpSRVVtYHODGHWHUPLQDomRVLPXOWkQHDGRSHVRPROHFXODU
QXPpULFRPpGLRGRSHVRPROHFXODUSRQGHUDOPpGLRHWDPEpPGDGLVWULEXLomRGH
SHVRPROHFXODU(VWDWpFQLFDWDPEpPpFRQKHFLGDFRPRFURPDWRJUDILDGHSHUPHDomR
HPJHO *3& FURPDWRJUDILDGHILOWUDomRHPJHOHWF

7.4.4.1 Mecanismo da separao


1D WpFQLFD GH H[FOXVmR SRU WDPDQKR D VHSDUDomR RFRUUH H[FOXVLYDPHQWH SRU
WDPDQKRPROHFXODU2PHFDQLVPRGHVHSDUDomRpLOXVWUDGRQD)LJXUD2UHFKHLR
GDV FROXQDV p FRQVWLWXtGR GH SDUWtFXODV FRQWHQGR SRURV GH GLYHUVRV WDPDQKRV 2
YROXPH WRWDO GD IDVH PyYHO FRUUHVSRQGH DR YROXPH GH SRURV 9S  PDLV R YROXPH
LQWHUVWLFLDO 9R  WDPEpP FRQKHFLGR FRPR YROXPH PRUWR 2 YROXPH GH SRURV p R
YROXPH RFXSDGR SHOD IDVH PyYHO HVWDJQDGD QRV SRURV H R YROXPH LQWHUVWLFLDO p R
YROXPHRFXSDGRSHODIDVHPyYHOIOXLQGRHQWUHDVSDUWtFXODV

)LJXUD0HFDQLVPRGHVHSDUDomRSRU6(&

&DUDFWHUL]DomRGH3ROtPHURV 
8PD VROXomR FRQWHQGR PROpFXODV GH SROtPHUR GH GLYHUVRV WDPDQKRV p LQMHWDGD
QDFROXQD0ROpFXODVFXMRWDPDQKRpPDLRUGRTXHRWDPDQKRGRVSRURVGRUHFKHLR
QmRFRQVHJXHPSHQHWUDURXVHGLIXQGLUQHVVHVSRURVHVmRWRWDOPHQWHH[FOXtGDVGRV
SRURV RX VHMD HODV QmR VmR UHWLGDV SHORV SRURV 2 YROXPH GH HOXLomR GHVVDV
PROpFXODV FRUUHVSRQGH DR YROXPH LQWHUVWLFLDO 9R  H SRU LVVR HODV VmR HOXtGDV
SULPHLUR 3RU RXWUR ODGR PROpFXODV PXLWR SHTXHQDV VmR FDSD]HV GH VH GLIXQGLU
FRPSOHWDPHQWH QRV SRURV GR UHFKHLR RX VHMD VmR FDSD]HV GH SHUPHDU WRWDOPHQWH
QR UHFKHLR 8PD PROpFXOD GHVVH WLSR QHFHVVLWD XPD TXDQWLGDGH EHP PDLRU GH
VROYHQWH SDUD DOFDQoDU D HOXLomR GD FROXQD 2 YROXPH GH HOXLomR GHVVDV PROpFXODV
FRUUHVSRQGHDRYROXPHLQWHUVWLFLDOPDLVRYROXPHGHSRURV 9R9S HSRULVVRHODV
VmR HOXtGDV SRU ~OWLPR 0ROpFXODV GH WDPDQKR PpGLR VmR FDSD]HV GH SHQHWUDU HP
DOJXQV SRURV SRUpP QmR HP WRGRV H R VHX YROXPH GH HOXLomR FRUUHVSRQGH D XP
YROXPH FRPSUHHQGLGR HQWUH R YROXPH WRWDO GD IDVH PyYHO 9R 9S  H R YROXPH
LQWHUVWLFLDO 9R 
2YROXPHGHHOXLomR 9H GHXPVROXWRpGDGRSHODVHJXLQWHHTXDomR
Ve = Vo + KV p (7.28)

RQGH.pRFRHILFLHQWHGHGLVWULEXLomRGRVROXWR2YDORUGH.VLWXDVHQDIDL[DHQWUH
H
.   RVROXWRpWRWDOPHQWHH[FOXtGRGRVSRURV
.   RVROXWRpWRWDOPHQWHSHUPHDGRQRVSRURV
.  IDL[DGHVHSDUDomR
%DVHDGR QHVWH SULQFtSLR GH VHSDUDomR QHQKXPD PROpFXOD SRGHULD HOXLU HP XP
YROXPH PHQRU GR TXH DTXHOH FRUUHVSRQGHQWH DR YROXPH LQWHUVWLFLDO RX HP XP
YROXPH PDLRU GR TXH DTXHOH FRUUHVSRQGHQWH j VRPD GR YROXPH LQWHUVWLFLDO H GR
YROXPHGHSRURV
2YROXPHWRWDOGHVROYHQWHFRQWLGRHPXPDFROXQDSDUD6(&pGLVWULEXtGRHQWUHR
YROXPHLQWHUVWLFLDOHRYROXPHGHSRURV(VWHVYROXPHVVmRSUDWLFDPHQWHLJXDLV3RU
H[HPSORXPDFROXQDGHVHSDUDomRSDUD6(&GRWLSRXOWUDVW\UDJHOIDEULFDGDSHOD
:DWHUV,QFFRQWpPDSUR[LPDGDPHQWHP/GHVROYHQWHGHQWURGRVSRURV YROXPH
GH SRURV  H  P/ GH VROYHQWH QRV LQWHUVWtFLRV HQWUH DV SDUWtFXODV TXH FRPS}HP R
UHFKHLR 3RUWDQWR XWLOL]DQGRVH HVWD FROXQD QHQKXPD PROpFXOD SRGHUi HOXLU DQWHV
GH  P/ RX GHSRLV GH  P/ 0ROpFXODV GH WDPDQKR LQWHUPHGLiULR HOXLUmR D XP
YROXPHHQWUHHP/
2 ORJDULWPR GR WDPDQKR PROHFXODU GD PDFURPROpFXOD p FRORFDGR HP JUiILFR
YHUVXVRYROXPHGHHOXLomRREWHQGRVHXPDFXUYDFRPRDLOXVWUDGDQD)LJXUD
0ROpFXODV PXLWR JUDQGHV VHUmR WRWDOPHQWH H[FOXtGDV GRV SRURV H HOXLUmR HP XP

 &URPDWRJUDILD
YROXPHFRUUHVSRQGHQWHDROLPLWHGHH[FOXVmR0ROpFXODVPXLWRSHTXHQDVSHUPHDUmR
HPWRGRVRVSRURVHHOXLUmRQRILQDOGRHYHQWRFURPDWRJUiILFR

)LJXUD'HSHQGrQFLDGRSHVRPROHFXODUFRPRYROXPHGHHOXLomRHPXPDFURPDWRJUDILDG HH[FOXVmRSRU
WDPDQKR

7.4.4.2. Tipos de fase estacionria para SEC


$IDVHHVWDFLRQiULDpDUHVSRQViYHOSHODVHSDUDomRFURPDWRJUiILFD3DUDRVXFHVVRGD
FURPDWRJUDILD GH H[FOXVmR SRU WDPDQKR D IDVH HVWDFLRQiULD GHYH SUHHQFKHU RV
UHTXLVLWRVGHVFULWRVDVHJXLUDOpPGDTXHOHVGHVFULWRVQRWySLFRUHODFLRQDGRVj
IRUPDHWDPDQKRGDVSDUWtFXODVHjSRURVLGDGH
 2 WDPDQKR GH SRURV GHYH VHU FRPSDUiYHO DR WDPDQKR GD PDFURPROpFXOD D VHU
DQDOLVDGD(VWDFRQGLomRpLQGLVSHQViYHOSDUDXPDERDVHSDUDomRSRU6(&
 $ GLVWULEXLomR GH WDPDQKR GH SRURV GHYH VHU GH WDO IRUPD TXH IRUQHoD XPD
GHSHQGrQFLDOLQHDUGRYROXPHGHHOXLomRFRPRORJDULWPRGRWDPDQKRPROHFXODU
GRVSROtPHURVLQYHVWLJDGRVRXVHMDDFXUYDGHFDOLEUDomRGHYHVHUOLQHDU
 $IDVHHVWDFLRQiULDQmRGHYHH[LELUTXDOTXHULQWHUDomRGRWLSRDGVRUomRFRPD
VXEVWkQFLDDVHUDQDOLVDGD
 $ IDVH HVWDFLRQiULD GHYH SRVVXLU UHVLVWrQFLD PHFkQLFD H HVWDELOLGDGH WpUPLFD H
TXtPLFD
'RLVWLSRVGHIDVHHVWDFLRQiULDSRGHPVHUXWLOL]DGRDVQDDQiOLVHGHSROtPHURVSRU
6(&SROtPHURPDFURSRURVRRXVLOLFDWRPDFURSRURVR2VVLOLFDWRVPDFURSRURVRVVmR

&DUDFWHUL]DomRGH3ROtPHURV 
UtJLGRV H QmR LQFKDP QD SUHVHQoD GR VROYHQWH 1HVWH FDVR R WDPDQKR GH SRUR
FRUUHVSRQGH DR WDPDQKR HIHWLYR GH SRURV TXH p GHWHUPLQDGR SRU SRURVLPHWULD GH
PHUF~ULRRXRXWUDWpFQLFDUHODFLRQDGD2WDPDQKRGHSRURVQmRpLQIOXHQFLDGRSHOD
WHPSHUDWXUDRXSHORVROYHQWH2VSROtPHURVPDFURSRURVRVXWLOL]DGRVFRPRUHFKHLR
SDUD6(&SRVVXHPHVWUXWXUDWULGLPHQVLRQDOQDVXDPDLRULDHVmRSUHSDUDGRVSRU
FRSROLPHUL]DomR RX SRU UHWLFXODomR GH PDFURPROpFXODV (VWHV PDWHULDLV SRGHP VHU
VHPLUtJLGRVRXGRWLSRVRIWJHO
2V UHFKHLRV VHPLUtJLGRV LQFKDP PXLWR SRXFR QD SUHVHQoD GR VROYHQWH 6XD
SRURVLGDGH p SRXFR DIHWDGD SHOR VROYHQWH 'HQWUH HOHV R PDLV XWLOL]DGR p DTXHOH
FRQVWLWXtGRGHFRSROtPHURUHWLFXODGRGHHVWLUHQRHGLYLQLOEHQ]HQR$GHVLJQDomRGH
WDPDQKR GH XPD FROXQD HP $QJVWURP  FRQWHQGR HVWH WLSR GH UHFKHLR QmR
FRUUHVSRQGH DR WDPDQKR QRPLQDO GH SRURV 1HVWH FDVR R WDPDQKR GH SRURV p
GHILQLGRFRPRRWDPDQKRGHXPDFDGHLDHVWHQGLGDGHXPDPROpFXODGHSROLHVWLUHQR
QR OLPLWH GD H[FOXVmR 3RU H[HPSOR XPD FROXQD FRQVWLWXtGD GH FRSROtPHUR GH
HVWLUHQRGLYLQLOEHQ]HQR GHVLJQDGD FRPR WHQGR XPD SRURVLGDGH LJXDO D c
FRQVHJXHVHSDUDUPROpFXODVFRPWDPDQKRVLQIHULRUHVDcDSHVDUGDVSDUWtFXODV
GRUHFKHLRSRVVXtUHPSRURVFRPWDPDQKRHIHWLYRGHc
 &RSROtPHURV GH HVWLUHQRGLYLQLOEHQ]HQR VmR PDWHULDLV DSRODUHV 6RE
FRQGLo}HV DSURSULDGDV HVWH UHFKHLR p FDSD] GH VHSDUDU RV FRPSRQHQWHV SHOR VHX
WDPDQKRPROHFXODUVHPDSUHVHQoDGRIHQ{PHQRGHDGVRUomR(VWHWLSRGHUHFKHLR
pRPDLVSRSXODUQDWpFQLFDGH6(&SRUTXHpFDSD]GHIUDFLRQDUSROtPHURVDSRODUHV
RXOLJHLUDPHQWHSRODUHVXWLOL]DQGRVHYiULRVWLSRVGHVROYHQWHVRUJkQLFRVFRPXQV

7.4.4.3. Seleo da coluna


&ROXQDV SDUD 6(& HVWmR GLVSRQtYHLV FRP YiULRV WDPDQKRV GH SRURV $ VHOHomR GR
WDPDQKRGHSRURVGHXPUHFKHLRHPXPDFROXQDSDUDFURPDWRJUDILDGRWLSR6(&
GHSHQGH GR WDPDQKR GDV PDFURPROpFXODV GR VROXWR D VHUHP DQDOLVDGDV 8PD
DPRVWUD GH SROtPHUR SRVVXL QD PDLRULD GRV FDVRV XP FRQMXQWR GH PROpFXODV GH
YiULRV WDPDQKRV  'HYLGR j YDULHGDGH GH WDPDQKR PROHFXODU HP XPD DPRVWUD GH
SROtPHURV p QHFHVViULR TXH R UHFKHLR GD FROXQD SRVVXD XPD YDULHGDGH JUDQGH GH
WDPDQKRGHSRURV,VWRpDOFDQoDGRXWLOL]DQGRVHYiULDVFROXQDVGLVSRVWDVHPVpULH
H FRP WDPDQKRV GH SRURV YDULDGRV $ )LJXUD  LOXVWUD FXUYDV GH FDOLEUDomR GH
FROXQDV FRP UHFKHLR GH FRSROtPHUR UHWLFXODGR GH HVWLUHQRGLYLQLOEHQ]HQR FRP
SRURVLGDGHV GLIHUHQWHV (VWDV FXUYDV GH FDOLEUDomR IRUDP REWLGDV XWLOL]DQGRVH
DPRVWUDV GH SROLHVWLUHQR GH WDPDQKRV PROHFXODUHV GLIHUHQWHV 2EVHUYDVH TXH R
OLPLWH GH H[FOXVmR DXPHQWD FRP R DXPHQWR GR WDPDQKR GH SRURV GR UHFKHLR GD
FROXQD 3RU RXWUR ODGR R WDPDQKR GDV PDFURPROpFXODV FDSD]HV GH SHUPHDU SRU
WRGRVRVSRURVGRUHFKHLRGDFROXQDDXPHQWDFRPRWDPDQKRGHSRURVGDFROXQD

 &URPDWRJUDILD
$ )LJXUD  LOXVWUD XP FURPDWRJUDPD GH XPD DPRVWUD FRQWHQGR SROLHVWLUHQR
GHYiULRVWDPDQKRVPROHFXODUHV3DUDVHDWLQJLUDVHSDUDomRIRLQHFHVViULRXWLOL]DU
WUrVFROXQDVFRPWDPDQKRVGHSRURVYDULDGRVHc

)LJXUD&XUYDVGHFDOLEUDomRSDUDFROXQDVXOWUDVW\UDJHOGD:DWHUV,QF IDVHHVWDFLRQiULD 
FRSROtPHURGHHVWLUHQRGLYLQLOEHQ]HQR 

)LJXUD&URPDWRJUDPDGHXPDPLVWXUDFRQWHQGRDPRVWUDVGHSROLHVWLUHQRSDGUmRGHYiULRVWDPDQKRV
PROHFXODUHV FROXQDVGHXOWUDVW\UDJHOGH Hc 

&DUDFWHUL]DomRGH3ROtPHURV 
7.4.4.4 Fase mvel
2VVROYHQWHVPDLVFRPXQVXWLOL]DGRVFRPRIDVHPyYHOHVWmRGHVFULWRVDVHJXLU
S7ROXHQR  HVWH VROYHQWH QmR DEVRUYH iJXD H QmR GHJUDGD FRP IDFLOLGDGH VHQGR
EDVWDQWHXWLOL]DGR&RPROLPLWDomRHOHQmRSRGHVHUXWLOL]DGRTXDQGRRVLVWHPD
GHGHWHFWRUHVpFRQVWLWXtGRSRUHVSHFWU{PHWURGHXOWUDYLROHWD$VXDSXULILFDomRp
VLPSOHVVHQGRVXILFLHQWHVHFDUFRPSHQHLUDPROHFXODU
S7HWUDKLGURIXUDQR  p R VROYHQWH PDLV FRPXP SRUTXH SRGH VHU XWLOL]DGR FRP
GHWHFWRUHV GH XOWUDYLROHWD H GH tQGLFH GH UHIUDomR (QWUHWDQWR HOH DEVRUYH iJXD
FRP PXLWD IDFLOLGDGH H SRU LVVR GHYH VHU VHFR FRP VyGLR H PDQWLGR HP
DWPRVIHUD LQHUWH GXUDQWH R IXQFLRQDPHQWR GR HTXLSDPHQWR $ SUHVHQoD GH
SHUy[LGRVQHVWHVROYHQWHQmRSRGHVHUGHVFDUWDGDeQHFHVViULRTXHVHXWLOL]HR
VROYHQWHUHFpPGHVWLODGRHTXHVHDGLFLRQHXPHVWDELOL]DQWHSDUDSHUy[LGRV
S&ORURIyUPLRHVWHVROYHQWHQmRDEVRUYHiJXDFRPWDQWDIDFLOLGDGHFRPRpRFDVR
GR WHWUDKLGURIXUDQR H SRGH VHU XWLOL]DGR FRP GHWHFWRUHV GH XOWUDYLROHWD
(QWUHWDQWR SRGH RFRUUHU GHFRPSRVLomR FRP RWHPSRFRPDOLEHUDomRGHiFLGR
FORUtGULFRH[WUHPDPHQWHSUHMXGLFLDOjVFROXQDV
SJXDiJXDpPXLWRXWLOL]DGDSDUDDDQiOLVHGHSROtPHURVKLGURVVRO~YHLV

7.4.4.5 A determinao do peso molecular pela tcnica SEC


$ FURPDWRJUDILD GH H[FOXVmR SRU WDPDQKR D H[HPSOR GH RXWUDV WpFQLFDV
FURPDWRJUiILFDVpXPDWpFQLFDGHVHSDUDomR3DUDTXHHVWDWpFQLFDVHMDXWLOL]DGDQD
GHWHUPLQDomRGHSHVRPROHFXODUGHXPDDPRVWUDSROLPpULFDpQHFHVViULRFRQVWUXLU
LQLFLDOPHQWHXPDFXUYDGHFDOLEUDomR3DUDWDQWRXWLOL]DPVHSDGU}HVGHSROtPHURV
PRQRGLVSHUVRV GH SHVRV PROHFXODUHV FRQKHFLGRV 2 SROtPHUR PDLV XWLOL]DGR FRPR
SDGUmRSDUDFURPDWRJUDILDGHH[FOXVmRSRUWDPDQKRpRSROLHVWLUHQRXPDYH]TXH
DPRVWUDV PRQRGLVSHUVDV FRP SHVR PROHFXODU GHILQLGR VmR IDFLOPHQWH REWLGDV
DWUDYpVGHSROLPHUL]DomRDQL{QLFD
$V DPRVWUDV GH SROLHVWLUHQR SDGUmR VmR DQDOLVDGDV SRU 6(& QDV PHVPDV
FRQGLo}HV HP TXH VHUmR DQDOLVDGDV DV DPRVWUDV GH SHVR PROHFXODU GHVFRQKHFLGR
$SyV D DQiOLVH FURPDWRJUiILFD R ORJDULWPR GR SHVR PROHFXODU GR SROLHVWLUHQR
XWLOL]DGR FRPR SDGUmR p FRORFDGR HP JUiILFR HP IXQomR GR YROXPH GH HOXLomR
REWHQGRVHXPDFXUYDVHPHOKDQWHjTXHODDSUHVHQWDGDQD)LJXUD
3DUD D GHWHUPLQDomR GRV SHVRV PROHFXODUHV QXPpULFR H SRQGHUDO PpGLRV
FRQVLGHUDVH TXH D DOWXUD GR FURPDWRJUDPD FRUUHVSRQGHQWH D FDGD YROXPH HOXtGR
KL VHMDSURSRUFLRQDOjTXDQWLGDGHGDTXHODIUDomRHPSHVRQDDPRVWUD
2SHVRPROHFXODUQXPpULFRPpGLR M n pGHILQLGRFRPR

 &URPDWRJUDILD
N i .M i
Mn = (7.29)
Ni
FRPR  
mi
Ni = e m i hi
Mi
HQWmR
hi
Mn = (7.30)
h
i
Mi
2SHVRPROHFXODUSRQGHUDOPpGLR M w pGHILQLGRFRPR

N i .M i2
Mw = (7.31)
N i .M i
RX  
hi .M i
Mw = (7.32)
hi
3DUD R FiOFXOR GH M n  M w  H GD SROLGLVSHUVmR 0:'  SURFHGHVH HQWmR jV
VHJXLQWHVHWDSDV
 WUDoDVHDOLQKDEDVHjFXUYD
 GLYLGHVHRFURPDWRJUDPDHPYiULRVLQFUHPHQWRVFRPRLOXVWUDGRQD)LJXUD
TXDQWRPDLRUIRUDGLYLVmRPDLVFRQILiYHOVHUiRUHVXOWDGR 
 PHGHVHDDOWXUDFRUUHVSRQGHQWHDFDGDYROXPHHOXtGR
 D SDUWLU GD FXUYD GH FDOLEUDomR GHWHUPLQDVH R YDORU GR SHVR PROHFXODU
FRUUHVSRQGHQWHDFDGDYROXPHHOXtGR
 PRQWDVHXPDWDEHODFRPRLOXVWUDGDQD7DEHODFRUUHODFLRQDQGRVHRYROXPH
HOXtGRFRPRSHVRPROHFXODUHDDOWXUDFRUUHVSRQGHQWH
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7.4.4.6 A calibrao universal


$WpFQLFDGHFURPDWRJUDILDGHH[FOXVmRSRUWDPDQKRUHODFLRQDRWHPSRRXYROXPH
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XP YROXPH PDLRU H HOXLUi HP PHQRU YROXPH GH HOXLomR GR TXH TXDQGR VH XWLOL]D
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e LPSRUWDQWH HQIDWL]DU TXH VH R FURPDWyJUDIR OtTXLGR HVWLYHU DFRSODGR D XP


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7.4.4.7 Aplicaes da cromatografia de excluso por tamanho na


caracterizao de polmeros
$ FURPDWRJUDILD GH H[FOXVmR SRU WDPDQKR HQFRQWUD YDVWD DSOLFDomR QD
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VHUiGHVFULWRDVHJXLU

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SEfeito da distribuio de peso molecular nas propriedades mecnicas
$ )LJXUD  LOXVWUD FURPDWRJUDPDV GH WUrV DPRVWUDV SROLPpULFDV GH XP PHVPR
PDWHULDO'HSHQGHQGRGDVFRQGLo}HVGHREWHQomRGRSROtPHURHVWHSRGHDSUHVHQWDU
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SEfeito das condies de processamento na degradao de um polmero


$ )LJXUD  DSUHVHQWD FXUYDV GH GLVWULEXLomR GH SHVR PROHFXODU GH DPRVWUDV GH
FRSROtPHURGHEXWDGLHQRHVWLUHQRHPIXQomRGRWHPSRGHPLVWXUD&RPRSRGHVHU
REVHUYDGR R SROtPHUR YLUJHP DSUHVHQWD XPD GLVWULEXLomR GH SHVR PROHFXODU
ELPRGDOFRQWHQGRXPDSHTXHQDIUDomRGHSHVRPROHFXODUEHPDOWR FXUYD (VWD
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PLVWXUDGRU GH FLOLQGURV DSUHVHQWD YDULDo}HV QD GLVWULEXLomR GR SHVR PROHFXODU 
PHGLGD TXH VH DXPHQWD R WHPSR GH PLVWXUD D IUDomR GH SHVR PROHFXODU PDLV
HOHYDGR YDL GLPLQXLQGR HQTXDQWR TXH D IUDomR SULQFLSDO GD DPRVWUD SHUPDQHFH
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)LJXUD&XUYDVGHGLVWULEXLomRGHSHVRPROHFXODUGHFRSROtPHURGHEXWDGLHQR HVWLUHQRHPIXQomRGR
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SControle de qualidade
8PPDWHULDOSROLPpULFRFRQWpPQDPDLRULDGRVFDVRVDGLWLYRVSDUDFRQIHULUPDLRU
IOH[LELOLGDGHHDLQGDHVWDELOL]DQWHVHDQWLR[LGDQWHV3DUDTXDQWLILFDUHVWHVDGLWLYRV
GH PDQHLUD UiSLGD UHFRPHQGDVH R XVR GD WpFQLFD GH 6(& XPD YH] TXH HVWHV
DGLWLYRV SRVVXHP SHVRV PROHFXODUHV EHP PDLV EDL[RV GR TXH R FRPSRQHQWH
SROLPpULFRSULQFLSDOHSRUWDQWRVmRIDFLOPHQWHVHSDUDGRVSRUHVWDWpFQLFD$)LJXUD
 LOXVWUD R FURPDWRJUDPD GH XPD DPRVWUD GH 39& FRQWHQGR SODVWLILFDQWH
FURPDWRJUDPDD 2SLFRpUHODWLYRDR39&GHYLGRDRDOWRSHVRPROHFXODUHRSLFR
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UHODomRHQWUHDViUHDVGRVSLFRVFKHJDVHjSURSRUomRGHSODVWLILFDQWHQDDPRVWUD
$OpP GLVVR D WpFQLFD p FDSD] GH IRUQHFHU LQIRUPDo}HV D UHVSHLWR GD QDWXUH]D
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FURPDWRJUDPDGHXPDPLVWXUDGHSRVVtYHLVSODVWLILFDQWHVQRUPDOPHQWHXVDGRVHP
IRUPXODo}HV GH 39& 2V SLFRV    H  UHIHUHPVH DRV SODVWLILFDQWHV IWDODWR GH
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SAcompanhamento de reao
$ WpFQLFD 6(& SRGH VHU WDPEpP XWLOL]DGD SDUD TXDQWLILFDU D IRUPDomR GH XP
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ILQDO GD UHDomR D PDLRU SDUWH GR PRQ{PHUR IRL FRQYHUWLGD HP SROtPHUR H R SLFR
UHODWLYRDRPRQ{PHURGHFUHVFHVXEVWDQFLDOPHQWH FXUYDF 

)LJXUD$FRPSDQKDPHQWRGHXPDUHDomRGHSROLPHUL]DomRDWUDYpVGDFURPDWRJUDILDGHH[FOXVmRSRU
WDPDQKR D ,QtFLRGDUHDomR E FRQYHUVmRSDUFLDOGHPRQ{PHURHPSROtPHUR F WpUPLQRGDUHDomR 

SDeterminao da composio de copolmeros


$PRVWUDV GH FRSROtPHURV DSUHVHQWDP QmR Vy GLVWULEXLomR GH SHVRV PROHFXODUHV
0:'  FRPR D PDLRULD GRV SROtPHURV PDV WDPEpP XPD GLVWULEXLomR QD
FRPSRVLomRTXtPLFD&RSROtPHURVGHSHVRVPROHFXODUHVVHPHOKDQWHVHFRPSRVLo}HV
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YROXPH KLGURGLQkPLFR DVVXPLGR SHOD PDFURPROpFXOD HP VROXomR R TXDO p IXQomR
GDVGLIHUHQoDVGHLQWHUDomRHQWUHDVFDGHLDVSROLPpULFDVHRVROYHQWHTXHFRQVWLWXLD
IDVH PyYHO $V FXUYDV FURPDWRJUiILFDV VHPSUH PRVWUDP D GLVWULEXLomR GH YROXPH
KLGURGLQkPLFR (P JHUDO VH WRGDV DV FDGHLDV GR FRSROtPHUR SRVVXtUHP PHVPD
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GHSHVRVPROHFXODUHV1DSUiWLFDRYROXPHKLGURGLQkPLFRGRVFRSROtPHURVGHSHQGH
GRSHVRPROHFXODUHGDFRPSRVLomRTXtPLFD
8PDGDVTXHVW}HVPDLVLPSRUWDQWHVQDDQiOLVHGHFRSROtPHURVSRU6(&pGHFLGLU
VH R YROXPH KLGURGLQkPLFR GHSHQGH GD FRPSRVLomR ,VWR SRGH VHU FRPSURYDGR
GHWHUPLQDQGRVHDYLVFRVLGDGHLQWUtQVHFDGHDPRVWUDVGRFRSROtPHURFRPGLIHUHQWHV
FRPSRVLo}HV TXtPLFDV H SHVRV PROHFXODUHV YDULDGRV 6H D GHSHQGrQFLD GD
YLVFRVLGDGHLQWUtQVHFDFRPRSHVRPROHFXODUSDUDFRSROtPHURVFRPFRPSRVLomRTXt
PLFDGLIHUHQWHGHURULJHPDXPDPHVPDUHWDSRGHVHGL]HUTXHSDUDRVLVWHPDHP
TXHVWmRDFRPSRVLomRQmRH[HUFHLQIOXrQFLDVLJQLILFDWLYDQRYROXPHKLGURGLQkPLFR
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GRLV GHWHFWRUHV TXH IRUQHoDP UHVSRVWD HP WHUPRV GH FRQFHQWUDomR H FRPSRVLomR
3DUDHVWHHVWXGRVmRXWLOL]DGRVXPGHWHFWRUGHtQGLFHGHUHIUDomRHXPEDVHDGRQD
HVSHFWURVFRSLD GH XOWUDYLROHWD e LPSRUWDQWH TXH XP GRV FRPSRQHQWHV GR
FRSROtPHURIRUQHoDVLQDOGLIHUHQFLDGRHPXPGRVGHWHFWRUHV
7RPHPRV FRPR H[HPSOR XP FRSROtPHUR GH HVWLUHQRDFULODWR GH PHWLOD $PERV
RV FRPSRQHQWHV GR FRSROtPHUR VmR YLVtYHLV DR GHWHFWRU GH tQGLFH GH UHIUDomR
(QWUHWDQWR XWLOL]DQGRVH R GHWHFWRU GH XOWUDYLROHWD GH FRPSULPHQWR GH RQGD IL[D
LJXDODQP VRPHQWHRFRPSRQHQWHHVWLUHQRpFDSD]GHVHUGHWHFWDGR
3DUD D GHWHUPLQDomR GD FRPSRVLomR GR FRSROtPHUR p QHFHVViULR DGTXLULU
DPRVWUDVSDGUmR GH GLIHUHQWHV FRPSRVLo}HV H DQDOLViODV SRU 6(& XWLOL]DQGRVH RV
GRLVGHWHFWRUHV2VLQDOIRUQHFLGRSRUDPERVRVGHWHFWRUHVpVHPSUHSURSRUFLRQDOj
FRQFHQWUDomR GD VXEVWkQFLD $SyV D DQiOLVH FRORFDVH HP JUiILFR D DOWXUD GR SLFR
IRUQHFLGR SRU FDGD GHWHFWRU HP IXQomR GD TXDQWLGDGH GH DFULODWR GH PHWLOD QD
DPRVWUD FRPR LOXVWUDGR QD )LJXUD  2 VLQDO IRUQHFLGR SHOR GHWHFWRU GH
XOWUDYLROHWDpUHODWLYRDSHQDVDRFRPSRQHQWHHVWLUHQR
&RQVLGHUHPRV R HVWLUHQR FRPR FRPSRQHQWH  H R DFULODWR GH PHWLOD FRPR
FRPSRQHQWH  2 VLQDO REWLGR D SDUWLU GR GHWHFWRU GH XOWUDYLROHWD p SURSRUFLRQDO j
IUDomRGHHVWLUHQRVHJXQGRD(TXDomR
RUV = c (1 w1 ) kUV ,2 (7.34)

RQGH F p D FRQFHQWUDomR GR FRSROtPHUR Z p D IUDomR HP PDVVD GR DFULODWR QR
FRSROtPHURHN89pDFRQWULEXLomRGRHVWLUHQRQRGHWHFWRUGHXOWUDYLROHWD
3RURXWURODGRRVLQDOREWLGRDSDUWLUGRGHWHFWRUGHtQGLFHGHUHIUDomRSRVVXLD
FRQWULEXLomRGHDPERVRVFRPSRQHQWHVFRPRH[SUHVVDD(TXDomR
RIR = c [w1 k IR ,1 + (1 w1 )k IR , 2 ] (7.35)

RQGHN,5HN,5VmRDFRQWULEXLomRGRDFULODWRHGRHVWLUHQRQRGHWHFWRUGHtQGLFHGH
UHIUDomRUHVSHFWLYDPHQWH

&DUDFWHUL]DomRGH3ROtPHURV 
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DFULODWRQRFRSROtPHUR

)LJXUD5HVSRVWDVGRVGHWHFWRUHVGHtQGLFHGHUHIUDomRHGHXOWUDYLROHWDUHODFLRQDGDVDFRSROtPHURGH
HVWLUHQRDFULODWRGHPHWLODHPIXQomRGDFRPSRVLomR

SCromatografia ortogonal
8PD DPRVWUD GH FRSROtPHUR TXH FRQWHQKD FDGHLDV FRP FRPSRVLomR TXtPLFD
GLIHUHQWHV SRGH VHU DQDOLVDGD XWLOL]DQGRVH XPD FRPELQDomR GH GXDV WpFQLFDV
FURPDWRJUiILFDV(VWDWpFQLFDFRQKHFLGDFRPRFURPDWRJUDILDRUWRJRQDOXWLOL]DGRLV
VLVWHPDVGH6(&$)LJXUDLOXVWUDDVHSDUDomRGHXPDDPRVWUDGHFRSROtPHURGH
HVWLUHQRPHWDFULODWRGHEXWLODSRUFRPSRVLomRXWLOL]DQGRVHGRLVVLVWHPDVGH6(&$
OHWUD$UHIHUHVHjXQLGDGHGHHVWLUHQRQRFRSROtPHURHDOHWUD%UHIHUHVHjXQLGDGH
GHPHWDFULODWRGHEXWLOD2SULPHLURVLVWHPDGH6(& 6(& XWLOL]DXPDIDVHPyYHO
WHWUDKLGURIXUDQR 7+)  TXH p XP ERP VROYHQWH SDUD R FRSROtPHUR 1HVWD SULPHLUD
IDVH D DPRVWUD p IUDFLRQDGD SHOR VHX WDPDQKR PROHFXODU $ DPRVWUD DR VDLU GR
SULPHLUR VLVWHPD GH 6(& p LQWURGX]LGD QR VLVWHPD GH LQMHomR GR VHJXQGR
FURPDWyJUDIR 6(&   (VWH VHJXQGR FURPDWyJUDIR WUDEDOKD FRP XPD IDVH PyYHO
FRQVWLWXtGD GH XPD PLVWXUD GH 7+) H QKHSWDQR 2 QKHSWDQR QmR p XP ERP
VROYHQWHSDUDRSROLHVWLUHQRORJRDVPROpFXODVULFDVHPHVWLUHQRVHHQFROKHUmRPDLV
QHVWD IDVH PyYHO H HOXLUmR D XP YROXPH EHP PDLRU GR TXH DTXHODV ULFDV HP
PHWDFULODWRGHEXWLOD

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)LJXUD(VTXHPDGHXPDFURPDWRJUDILDRUWRJRQDOGHXPFRSROtPHURTXHPRVWUDR IUDFLRQDPHQWRSRU
WDPDQKR 6(& HSRUFRPSRVLomR 6(& 

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9.3.2 Programador de temperatura do forno


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9.3.5 Cadinho (ou porta amostra)


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S(VWDEHOHFHUQRFRPSXWDGRUDVWHPSHUDWXUDVLQLFLDOHILQDOGDDQiOLVHHD
YHORFLGDGH GHYDULDomR GHWHPSHUDWXUD RXSDUD R PRGR LVRWpUPLFR IRUQHFHU D
WHPSHUDWXUD HRWHPSR GH DQiOLVH
S&RORFDU RFDGLQKR YD]LR QR HTXLSDPHQWR HSRU PHLR GR FRPSXWDGRU DFLRQDU R
FRPDQGR SDUD]HUDU DPDVVD GRFDGLQKR
S5HWLUDU R FDGLQKR GR HTXLSDPHQWR SUHHQFKrOR FRP DPRVWUD H UHFRORFiOR QR
HTXLSDPHQWR
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S$FLRQDU XWLOL]DQGR R FRPSXWDGRU RFRPDQGR SDUD LQLFLDUDDQiOLVH
S$R WHUPLQDU DDQiOLVH UHWLUDURFDGLQKR H
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DQiOLVH

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GH PDVVD YHUVXV
WHPSHUDWXUD RXWHPSR 
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GPGW YHUVXV
WHPSR 

2VWLSRVGH
FXUYDV
GH7* HVWmR
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GXUDQWH R
H[SHULPHQWRpUHFRPHQGDGR TXH RIRUQRVHMDDTXHFLGRDWp
 .DFLPD
GD
IDL[DGHWHPSHUDWXUDVHOHFLRQDGD

9.6 Aplicaes gerais da termogravimetria


$WHUPRJUDYLPHWULDpPXLWRXWLOL]DGDQDVPDLVGLYHUVDViUHDVWDLVFRPRDGH
TXtPLFDHDGH JHRORJLD$V DSOLFDo}HVHVSHFtILFDVGDWHUPRJUDYLPHWULDSRGHPVHU
UHVXPLGDVQRV WySLFRVDSUHVHQWDGRV DVHJXLU
S'HFRPSRVLomR WpUPLFD GH VXEVWkQFLDV LQRUJkQLFDVRUJkQLFDV
GH EDL[DPDVVD
PRODUHGHSROtPHURV GHWHUPLQDomR GDWHPSHUDWXUD GHGHFRPSRVLomR
S3LUyOLVH
GH GLYHUVDVVXEVWkQFLDV
S'HWHUPLQDomR GHXPLGDGH WHRUGHYROiWHLV
HGHFLQ]DV
S(VWXGRV GHGHJUDGDomR HKLJURVFRSLFLGDGH
S2[LGDomR WpUPLFD GHJUDGDWLYD GH
VXEVWkQFLDV SROLPpULFDV
S(VWXGRV FLQpWLFRVGHUHDo}HV
S&XUYDV GHDGVRUomR HGHVVRUomR

9.7 Degradao trmica de polmeros


6HUiDSUHVHQWDGDDVHJXLUXPDEUHYHDERUGDJHPWHyULFDVREUHDGHJUDGDomR
WpUPLFD GH SROtPHURV QHFHVViULD SDUD R PHOKRU HQWHQGLPHQWR GHGHWHUPLQDGRV
DVSHFWRV GDLQWHUSUHWDomR GHFXUYDV GH 7*PRVWUDGRV QRVH[HPSORV GHDSOLFDo}HV GR
PpWRGR RUD GHVFULWR 
3ROtPHURV QDWXUDLV HVLQWpWLFRVSRGHP DSUHVHQWDU FHUWDLQVWDELOLGDGH TXtPLFD VRE
DDomRGHGHWHUPLQDGRVDJHQWHV(QWUHHVVHVSRGHPVHUFLWDGRVUDGLDo}HV
HOHWURPDJQpWLFDV UDLRVJDPDLQIUDYHUPHOKDXOWUDYLROHWDHWF HFLVDOKDPHQWR
3RUpP RHIHLWR GR FDORUVREUH DHVWDELOLGDGHGH PDWHULDLV SROLPpULFRV pRSURFHVVR
GH PDLRU LQWHUHVVH HRPDLV H[WHQVLYDPHQWH HVWXGDGR 1D VXD JUDQGH PDLRULDRV
PDWHULDLV SROLPpULFRV VmRVXEPHWLGRV DWHPSHUDWXUDV HOHYDGDV FRPR pRFDVR GH
SOiVWLFRVHHODVW{PHURVXVDGRVQDLQG~VWULDDXWRPRWLYDXWHQVtOLRVGRPpVWLFRV
DGLWLYRV SROLPpULFRV SDUDPLVWXUD DVIiOWLFDRXSDUDIOXLGRV GHUHFXSHUDomR GHSRoRV
GH SHWUyOHR HHP LQ~PHUDV RXWUDV DSOLFDo}HV2VSROtPHURV TXDQGR VXEPHWLGRV D
XP WUDWDPHQWR WpUPLFR SRGHP DSUHVHQWDU PXGDQoDV HVWUXWXUDLV FDUDFWHUL]DGDV SRU
UXSWXUD GHOLJDo}HV TXtPLFDV QDVFDGHLDV SULQFLSDO
HODWHUDLV(VVDVPRGLILFDo}HV VmR
HYLGHQFLDGDV SHODGLPLQXLomR QD PDVVD PRODUFRP HYROXomR GHSURGXWRV YROiWHLV

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:DDOV
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OLJDo}HV
KLGURJrQLR

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SJUDX GHOLJDo}HV FUX]DGDV HUDPLILFDo}HV


2VIDWRUHV
ItVLFRVFRPSUHHQGHP 
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SLQWHUDo}HV
PROHFXODUHV HIHLWRGLSRODU 

SSXUH]D

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YDULDGDVTXDQGR VXEPHWLGRV DGHWHUPLQDGDV YDULDo}HVGH WHPSHUDWXUD $VHWDSDV
TXtPLFDV HQYROYLGDV QD IRUPDomR GRV SURGXWRV YROiWHLVSRGHP GLIHULU
HP QDWXUH]D
HOHWU{QLFDYLDUDGLFDLV OLYUHVRXL{QLFD'HDFRUGR FRP RVWLSRVGH SURGXWRVYROiWHLV
JHUDGRVRV PDWHULDLV SROLPpULFRV SRGHP VHUFODVVLILFDGRVHP SROtPHURV TXH

SGHVSROLPHUL]DP
SQmR GHVSROLPHUL]DP
SVRIUHP UHDo}HV LQWUD H
LQWHUPROHFXODUHV

9.7.1 Polmeros que despolimerizam


3DUD RV SROtPHURV TXH GHVSROLPHUL]DP RSURFHVVR GHGHJUDGDomR RFRUUHDWUDYpVGH
FOLYDJHPDOHDWyULDGDFDGHLDVHJXLGDGHGHVSROLPHUL]DomR(VWHSURFHVVRp
FDUDFWHUL]DGR SRUUHQGLPHQWRV HOHYDGRV GHPRQ{PHUR QRVSURGXWRV GHGHJUDGDomR
HGHFUpVFLPR OHQWRQD PDVVD PRODU GRSROtPHUR
$GHJUDGDomRWpUPLFDGRSROL PHWDFULODWRGHPHWLOD  300$ RFRUUHSRU
GHVSROLPHUL]DomR SURGX]LQGR TXDVH TXH  GHPRQ{PHUR eXP SURFHVVRYLD
UDGLFDLV OLYUHVHpHVVHQFLDOPHQWH RLQYHUVRGD UHDomRGHSROLPHUL]DomR 1D)LJXUD
HVWi UHSUHVHQWDGR RSURFHVVR GHGHJUDGDomR GR300$ (VVDGHJUDGDomR RFRUUH
SRU PHLR GDFLVmR DOHDWyULDGD FDGHLD HQmRpDFRPSDQKDGD SRU WUDQVIHUrQFLDGH
KLGURJrQLR QRVtWLRGDFLVmRGHYLGRDR LPSHGLPHQWR HVSDFLDO
GRVJUXSDPHQWRV &+H
&22&+'HVWHPRGRDFLVmRUHVXOWDQDIRUPDomRGHGRLVUDGLFDLVOLYUHVTXH
RFDVLRQD HQWmR DGHVSROLPHUL]DomR (VWHSURFHVVR GHGHJUDGDomR DSDUHFH QDFXUYD
GH 7*LOXVWUDGD QD )LJXUD
HP XP ~QLFRHVWiJLR

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GH
3ROtPHURV 
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UDGLFDLVOLYUHV

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$VVLP FRPRR300$R SROLHVWLUHQR 36 WDPEpPGHVSROLPHUL]DYLD


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SRUpP HP
SRUFHQWDJHQVEHPLQIHULRUHV$SHQDVFHUFDGHGHHVWLUHQRpIRUPDGRGD

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$ FRPSDUDomR GDSRUFHQWDJHP GH SURGXomR GH PRQ{PHUR DSDUWLU GHSROtPHURV
GH HVWLUHQR  HGHXWHURHVWLUHQR HPHWLO HVWLUHQR PRVWUD FODUDPHQWH TXH R
iWRPR GHKLGURJrQLR  pR TXH HVWi HQYROYLGR QR SURFHVVR GH WUDQVIHUrQFLD GH
FDGHLD 6XD VXEVWLWXLomR SRU GHXWpULR GLPLQXL D WUDQVIHUrQFLD HQTXDQWR TXH VXD
VXEVWLWXLomR SRU XP JUXSR PHWLODHOLPLQD FRPSOHWDPHQWH DUHDomR GH WUDQVIHUrQFLD
2SROL PHWLO HVWLUHQR ILJXUDHQWUH RVSROtPHURV TXH SURGX]HP TXDVH TXH  GH
PRQ{PHUR 2XWURVSROtPHURV TXH DSUHVHQWDP RPHVPR WLSRGH GHJUDGDomR DOpP GR
300$ MiPHQFLRQDGR LQFOXHP D SROLPHWDFULORQLWULOD RSROL FLDQHWR GH YLQLOLGHQR  H
R
RSROL WHWUDIOXRURHWLOHQR (VWH~OWLPR VRIUH SURFHVVR GHSLUyOLVH HQWUH  H &

9.7.2 Polmeros que no despolimerizam


3DUDRVSROtPHURVTXHQmRGHVSROLPHUL]DPDGHJUDGDomRRFRUUHSRUPHLRGD
FOLYDJHP DOHDWyULD GDFDGHLD VHJXLGD SRURXWUDV FOLYDJHQV DRDFDVR TXH OHYDP D
XPD SURGXomR GH PRQ{PHURV EDL[D HDXP UiSLGR GHFUpVFLPR QDPDVVD PRODU
&RPR H[HPSOR GHVWDFODVVH GHSROtPHURV SRGHP VHUFLWDGDVDV SROLROHILQDVTXH
UHSUHVHQWDP  GDSURGXomR PXQGLDO GH SOiVWLFRV GHQWUH DVTXDLV VHGHVWDFDD
SURGXomRGHSROLHWLOHQRGHDOWDGHQVLGDGH 3($' XWLOL]DGRSULQFLSDOPHQWHQD
PDQXIDWXUD GH SHoDV PROGDGDV HSROLHWLOHQR GH EDL[D GHQVLGDGH 3(%'  XPD GDV
SULQFLSDLV PDWpULDVSULPDV GDLQG~VWULD GH
HPEDODJHQV SHORVHXUHODWLYR EDL[RFXVWR
H SRUVHU TXLPLFDPHQWH LQHUWH $HVWDELOLGDGH WpUPLFD GR3( HVWi UHODFLRQDGD DR
JUDXHQDWXUH]DGDVUDPLILFDo}HV23($'TXHSUDWLFDPHQWHQmRSRVVXL
UDPLILFDo}HV p WHUPLFDPHQWH PDLV HVWiYHO TXH R 3(%' TXH SRVVXL XP JUDX GH
UDPLILFDo}HV VLJQLILFDWLYRTXDQGR FRPSDUDGR DR3($' 2 SURFHVVR GHGHJUDGDomR GR
3( SURGX] XPD JUDQGH TXDQWLGDGH GH PRQRROHILQDV GDV TXDLVDVPDLV DEXQGDQWHV
VmRRSURSHQRHRKH[HQR2PHFDQLVPRSULQFLSDOGHGHJUDGDomRpDFLVmR
KRPROtWLFD GD FDGHLD HDVUHDo}HV GH WUDQVIHUrQFLD RFRUUHP PDLV UDSLGDPHQWH QRV
iWRPRVGHKLGURJrQLRVOLJDGRVDiWRPRVGHFDUERQRWHUFLiULRV$FLVmRLQLFLDO
HQYROYH OLJDo}HV && SRQWRV GH UDPLILFDomR FRPR RFRUUH QR 3(%'  RX RXWUDV
OLJDo}HVIUDFDV TXH SRGHP WHUVLGRIRUPDGDV GXUDQWH RSURFHVVR GHSROLPHUL]DomR 
2XWURV GRLV H[HPSORV GHSROtPHURV TXH QmR GHVSROLPHUL]DP VmR RSROL y[LGRGH
HWLOHQR  3(2 HRSROL y[LGRGHSURSLOHQR  332 $GHJUDGDomRWpUPLFDGHVVHV
SROtPHURVSURGX]TXDQWLGDGHVPXLWRSHTXHQDVGRVUHVSHFWLYRVPRQ{PHURV$
GHJUDGDomR WpUPLFD GRSROL y[LGR GH HWLOHQR  SURGX] HP PDLRU SURSRUomR DOpP GR
y[LGRGHHWLOHQR a IRUPDOGHtGRHWDQROGLy[LGRGHFDUERQRHiJXD-iR

&DUDFWHUL]DomR
GH
3ROtPHURV 
SROL y[LGR GHSURSLOHQR  SURGX] DOpP GR y[LGR GH SURSLOHQR a  XPD JDPD
PDLRU GH FRPSRVWRV SUHVHQWHV HP TXDQWLGDGHV VLJQLILFDWLYDVDFHWDOGHtGR SURSHQR
DFHWRQD pWHUGLSURStOLFR pWHUHWLOLVRSURStOLFR PHWLOHWLOFHWRQD LVRSURSDQRO HQWUH
RXWURV +i XPD SHTXHQD GLIHUHQoD QD HVWDELOLGDGH WpUPLFD GHVWHV GRLV SROLy[LGRV
VHQGR R 3(2 PDLV HVWiYHO TXH R332 (VWH IDWRHQWUH RXWURVOHYD jFRQFOXVmR TXH
iWRPRV GH FDUERQR WHUFLiULRVHTXDWHUQiULRV QDFDGHLD LQWURGX]HP SRQWRV IUDFRV QD
HVWUXWXUD GRSROtPHUR 3RU RXWURODGR SROLHWLOHQR HSROLSURSLOHQR VmR WHUPLFDPHQWH
PDLV HVWiYHLV TXHVHXV UHVSHFWLYRV pWHUHVLVWR p
DLQWURGXomR GH R[LJrQLR QD FDGHLD
KLGURFDUE{QLFD GR SROtPHUR UHGX] DHVWDELOLGDGH WpUPLFD SRUTXH DOLJDomR &2 p
PDLV IUDFD TXH DOLJDomR && $ VHJXLQWH RUGHP GH HVWDELOLGDGH WpUPLFD SRGH
HQWmRVHU HVWDEHOHFLGD
PPO < PEO < PP < PE

9.7.3 Polmeros que sofrem reaes intra- e intermoleculares


1R FDVR GH SROtPHURV TXH VRIUHP UHDo}HV LQWUD H LQWHUPROHFXODUHV RFRUUH XPD
UHDomR TXtPLFD LQWUDPROHFXODU VHJXLGD SRUXPD UHDomR GH UHWLFXODomR HFOLYDJHP
DOHDWyULDGDFDGHLD FRP JHUDomR GHDOWRWHRUGHYROiWHLV
(PFRQWUDVWHFRPR300$QRVGHPDLVSROLPHWDFULODWRVSRGHRFRUUHUD
GHFRPSRVLomR GR JUXSR pVWHU
3DUDR SROL PHWDFULODWR GHWHUWEXWLOD SRU H[HPSOR D
UHDomR RFRUUH SRU XP PHFDQLVPR TXH HQYROYH D LQWHUDomR HQWUH R JUXSDPHQWR
FDUERQLOD H
RViWRPRV GHKLGURJrQLR GRiWRPR GHFDUERQR GR JUXSR pVWHU )LJXUD
 
2 SULQFLSDO IDWRUTXH GHWHUPLQD DSUHGRPLQkQFLD GD GHVSROLPHUL]DomR RXGD
GHFRPSRVLomR GR pVWHUpDUHODWLYD
IDFLOLGDGH GHWDOLQWHUDomR LVWRpDGHFRPSRVLomR
GRJUXSRpVWHUWRUQDVHLPSRUWDQWHVRPHQWHTXDQGRDXQLGDGHPRQRPpULFD
DSUHVHQWDSHORPHQRViWRPRVGHKLGURJrQLRQRiWRPRGHFDUERQR(VWH
PHFDQLVPR GHGHJUDGDomR HDSUHVHQWDGR QD FXUYD GH 7* GD )LJXUD FRPR XP
SURFHVVR HP GRLVHVWiJLRV

)LJXUD3URFHVVRGHGHFRPSRVLomRGRJUXSRpVWHUGRSROL PHWDFULODWRGHWHUWEXWLOD HQYROYHQGRXPDQHO


GHVHLVPHPEURV

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3$0$ HSROL PHWDFULODWRGHGHWEXWLOD  3W%0$ 

8P H[HPSOR LPSRUWDQWH GH SROtPHUR GHVWD FODVVH pRSROL FORUHWRGHYLQLOD 


39& 
$SHVDU GHVWHSROtPHUR VHUWDOYH] RPDLV HVWXGDGR TXDQWR j VXDGHFRPSRVLomR VHX
PHFDQLVPR GHGHJUDGDomR DLQGD QmR pPXLWR EHP HVFODUHFLGR$ WD[DGH IRUPDomR
GH+&OpPXLWRGHSHQGHQWHGDVFRQGLo}HVH[SHULPHQWDLV*UDQGHSDUWHGD
GLVFRUGkQFLDH[LVWHQWHVREUHRPHFDQLVPRGDUHDomRGHYHVHDRIDWRGHTXH
SROtPHURVSUHSDUDGRVHPFRQGLo}HVGLIHUHQWHVIRUDPHVWXGDGRVVREFRQGLo}HV
H[SHULPHQWDLV GH GHJUDGDomR GLIHUHQWHV H JHUDUDP UHVXOWDGRV WDPEpP GLIHUHQWHV
'H XP PRGR JHUDO DGHFRPSRVLomR RFRUUH DWUDYpV GH XPD UHDomR LQWUDPROHFXODU
TXHHQYROYHGHVKLGURKDORJHQDomRHIRUPDomRGHXPSROLHQR2VSURGXWRVGD
GHJUDGDomRWpUPLFDGR39&VmRRiFLGRFORUtGULFRHXPUHVtGXRDOWDPHQWH
FRQMXJDGR &RPR PHFDQLVPRV GH GHFRPSRVLomR VmR SURSRVWRV WDQWR RPROHFXODU
FRPR RYLDUDGLFDLVOLYUHV
2 HQWHQGLPHQWR FRPSOHWR GR PHFDQLVPR HQYROYLGR QDGHJUDGDomR WpUPLFD GH
SROtPHURV UHTXHUR FRQKHFLPHQWR GHWUrVSRQWRV IXQGDPHQWDLV
DYDULDomR GDPDVVD PRODU GRSROtPHUR HP IXQomR GDWHPSHUDWXUD HHYROXomR GR
SURFHVVR GHGHJUDGDomR 
DFRPSRVLomR TXDOLWDWLYD HTXDQWLWDWLYD GRV SURGXWRV GH GHJUDGDomR YROiWHLVH
QmRYROiWHLVH
DVYHORFLGDGHV HHQHUJLDV GHDWLYDomR GRSURFHVVR GHGHJUDGDomR

&DUDFWHUL]DomR
GH
3ROtPHURV 
9.8 Exemplos de curvas de TG tpicas e aplicaes no estudo de
polmeros
9.8.1 Estabilidade trmica de polmeros
$WHUPRJUDYLPHWULD SRGHVHUXVDGD VLPSOHVPHQWH SDUD
GHWHUPLQDU DWHPSHUDWXUD GH
GHFRPSRVLomR GH GLYHUVRVSROtPHURV 2X DLQGDSDUDUHDOL]DU HVWXGRVHVSHFtILFRV
FRPR SRU H[HPSOR GHHVWDELOLGDGHGH SROtPHURVFRQWHQGR IO~RURDXPHQWR GR WHRU
GHIO~RU QD PROpFXOD DXPHQWD D
HVWDELOLGDGHWpUPLFDGR PDWHULDO 1D)LJXUD 
REVHUYDVHTXHRSROL WHWUDIOXRURHWLOHQR pWHUPLFDPHQWHPDLVUHVLVWHQWHTXHR
SROLHWLOHQR8PD H[FHomRREVHUYDGD QHVWHFDVR
HTXHWDPEpP pPRVWUDGD QD)LJXUD
p DHVWDELOLGDGHWpUPLFD GRSROL KH[DIOXRURSURSLOHQR  TXH pPHQRU TXH D GR
SROLSURSLOHQR

9.8.2 Estabilidade trmica de polmeros em funo da massa molar


$HVWDELOLGDGH WpUPLFD GH PDWHULDLVSROLPpULFRV SRGH YDULDUHP IXQomR GDVXD PDVVD
PRODU 8P H[HPSOR EDVWDQWH FODUR GLVWRp HQFRQWUDGR QDV FXUYDVGH GHJUDGDomR
WpUPLFDGRSROL GLPHWLOVLOR[DQR $PRVWUDVGHPDVVDPRODUQXPpULFDPpGLDGH
   H  DSUHVHQWDP XPD GLIHUHQoD GHHVWDELOLGDGH WpUPLFD
R
GH FHUFDGH & DXPHQWDQGR FRP RDXPHQWR GDPDVVD PRODU eEDVWDQWH UD]RiYHO
HQFRQWUDU XPD H[SOLFDomR SDUD HVWH IDWROHYDQGRVH HP FRQWDD PDLRU VXVFHSWL
ELOLGDGHGRV WHUPLQDLV GH FDGHLDjGHJUDGDomR $VVLP TXDQWR PHQRU D PDVVD PRODU
PDLRU RQ~PHUR GH WHUPLQDLV GHFDGHLDV HPHQRU D HVWDELOLGDGHWpUPLFD eLP
SRUWDQWH VDOLHQWDU TXHH[LVWHXPD WHQGrQFLD GDHVWDELOLGDGH WpUPLFDPDQWHUVH TXD
VHTXH FRQVWDQWH DSDUWLUGHGHWHUPLQDGD PDVVD PRODU GD DPRVWUDTXDQGR RWDPD
QKR GDFDGHLD MipJUDQGH R
VXILFLHQWHSDUDWRUQDU TXDVH TXH GHVSUH]tYHODLQIOXrQFLD
GRV WHUPLQDLV GHFDGHLD (VVHYDORUGH PDVVD PRODU YDULDGH SROtPHURSDUD SROtPHUR
HQRUPDOPHQWH pGHWHUPLQDGD H[SHULPHQWDOPHQWH

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9.8.3 Estabilidade trmica do poli(metacrilato de metila) (PMMA) em funo


da razo metacrilato de metil/azobisisobutironitrila (MMA/AIBN) na
polimerizao via radicais livres
8PD RXWUD IRUWHLQIOXrQFLD GRVWHUPLQDLVGH FDGHLDQDWHPSHUDWXUD HPHFDQLVPR GH
GHJUDGDomRGHXPSROtPHURpREVHUYDGDDRDQDOLVDUGXDVDPRVWUDVGH
SROL PHWDFULODWR GH PHWLOD  300$  REWLGDV YLDUDGLFDLVOLYUHVSRUpP FRP FRQFHQ
WUDo}HV GH LQLFLDGRU D]RELVLVREXWLURQLWULOD $,%1 GLIHUHQWHV 8VDQGRVH SHTXHQD
TXDQWLGDGH GH LQLFLDGRU DDPRVWUD VLQWHWL]DGD DSUHVHQWDUi XPD FXUYDGHGHJUD
GDomR WtSLFDGR 300$ LVWRp
HP DSHQDV HVWiJLR$DPRVWUD VLQWHWL]DGDDSDUWLUGH
XPD HOHYDGD FRQFHQWUDomR GHLQLFLDGRUJHUDQGR FDGHLDV PHQRUHV HPDLRU GLVWUL
EXLomR GHWDPDQKR GDVFDGHLDVDSUHVHQWDUi XPDWHPSHUDWXUD LQLFLDOGH
GHJUDGDomR
PHQRU HXP PHFDQLVPR GHGHFRPSRVLomR GLIHUHQWHR TXH pUHIOHWLGRQDFXUYD HP
PDLVGH XPD HWDSD

9.8.4 Caracterizao de copolmeros em bloco versus aleatrio de estireno


e -metil estireno
$DQiOLVHWHUPRJUDYLPpWULFD
GHDPRVWUDVGHSROLHVWLUHQR 36 SROL PHWLO
HVWLUHQR 
3P6 H RV
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GHJUDGDomR GRSROtPHUR

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9.8.7 Curvas de TG de homopolmeros e copolmeros


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9.9 TG em sistemas acoplados


ePXLWR
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9.10 Reaes de recombinao no porta amostra


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Anlise Trmica Diferencial


(DTA) e Calorimetria
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(DSC)

10.1 Introduo
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WHPSHUDWXUD 2 UHJLVWUR IRUQHFH VRPHQWH RV YDORUHV GDV WHPSHUDWXUDV QDV TXDLV
RFRUUHP DV PXGDQoDV QD DPRVWUD H VH HVVDV WUDQVIRUPDo}HV VmR HQGRWpUPLFDV RX
H[RWpUPLFDVRXDLQGDVHRFRUUHDSHQDVXPDYDULDomRQDFDSDFLGDGHFDORUtILFD
$PDJQLWXGHGH7DXPGHWHUPLQDGRWHPSRpSURSRUFLRQDOD
SYDULDomRGHHQWDOSLD
SFDSDFLGDGHFDORUtILFDH
SUHVLVWrQFLDWpUPLFDWRWDODRIOX[RGHFDORU5

$ DOWD VHQVLELOLGDGH GR HTXLSDPHQWR UHTXHU TXH R YDORU GH 5 VHMD JUDQGH
,QIHOL]PHQWH HVWH YDORU GHSHQGH GD QDWXUH]D GD DPRVWUD GD IRUPD SHOD TXDO IRL
HPSDFRWDGD QR SRUWDDPRVWUD H GD HILFLrQFLD GR FRQWDWR WpUPLFR HQWUH R SRUWD
DPRVWUD H R FRPSDUWLPHQWR GD DPRVWUD 5 WDPEpP YDULD FRP D WHPSHUDWXUD $
QHFHVVLGDGHGHVHUFRQVLGHUDGDDLQIOXrQFLDGHVVHVIDWRUHVLQYLDELOL]DDFRQYHUVmRGD
iUHD GR SLFR HP XQLGDGHV GH HQHUJLD 2 SLFR p UHJLVWUDGR HP XP JUiILFR RQGH D
YDULDomRGH7pFRORFDGDHPIXQomRGDWHPSHUDWXUDRXGRWHPSR

&DUDFWHUL]DomRGH3ROtPHURV  
10.3 Calorimetria diferencial de varredura (DSC)
10.3.1 Comparao com o DTA
3DUD VXSULU D FDUrQFLD GH LQIRUPDo}HV GR '7$ IRL GHVHQYROYLGR XP SURFHGLPHQWR
DOWHUQDWLYR FRQKHFLGR FRPR FDORULPHWULD GLIHUHQFLDO GH YDUUHGXUD '6&  $V FXUYDV
REWLGDVSRUPHLRGHVWDWpFQLFDVmRVLPLODUHVjVGR'7$PDVUHSUHVHQWDPUHDOPHQWH
DTXDQWLGDGHGHHQHUJLDHOpWULFDIRUQHFLGDSDUDRVLVWHPDHQmRDSHQDV7$VVLP
DViUHDVVRERVSLFRVVHUmRSURSRUFLRQDLVjVYDULDo}HVGHHQWDOSLDTXHRFRUUHPHP
FDGD WUDQVIRUPDomR $ FDOLEUDomR GR LQVWUXPHQWR LUi SHUPLWLU D GHWHUPLQDomR
TXDQWLWDWLYD GD FDSDFLGDGH FDORUtILFD GH XPD DPRVWUD ,VWR p REWLGR ID]HQGR XPD
DQiOLVH HP TXH D DPRVWUD p XPD VXEVWkQFLD SDGUmR LVWR p WHP RV YDORUHV GD
WHPSHUDWXUD GH IXVmR H GR FDORU GH IXVmR EHP GHWHUPLQDGRV H SDGURQL]DGRV 6mR
XVDGRVSDUDHVWDILQDOLGDGHiJXDVXEVWkQFLDVRUJkQLFDVHPHWDLVFRPRtQGLR ,Q H
HVWDQKR 6Q 2SURFHGLPHQWRGHFDOLEUDomRVHUiGHWDOKDGRPDLVDGLDQWH
3HUFHEHVHGHVWHPRGRTXHDWpFQLFDGH'6&IRUQHFHPDLVLQIRUPDo}HVGRTXHD
GH '7$ $VVLP VHUi GLVFXWLGR FRP XP SRXFR PDLV GH GHWDOKHV R '6& GH PRGR D
HQWHQGHUFRPRHVVDVLQIRUPDo}HVDGLFLRQDLVVmRREWLGDV
$)LJXUDPRVWUDRGLDJUDPDGRVFRPSDUWLPHQWRVGDDPRVWUD $ HUHIHUrQFLD
5  FRP IRQWHV GH DTXHFLPHQWR LQGLYLGXDLV HP TXH D WHPSHUDWXUD H D HQHUJLD VmR
PRQLWRUDGDV H JHUDGDV SRU ILODPHQWRV GH SODWLQD LGrQWLFRV TXH DWXDP FRPR
WHUP{PHWURVUHVLVWLYRVHDTXHFHGRUHV

)LJXUD'LDJUDPDHVTXHPiWLFRGRFRPSDUWLPHQWRGDDPRVWUDQDDQiOLVH'6&

(VWD WpFQLFD PDQWpP FRQVWDQWH R FDORU IRUQHFLGR 3RUpP DR LQYpV GH PHGLU D
GLIHUHQoD GH WHPSHUDWXUD GXUDQWH D WUDQVIRUPDomR TXH RFRUUH QD DPRVWUD XP
VLVWHPD GH FRQWUROH VHUYRVLVWHPD  DXPHQWD LPHGLDWDPHQWH D HQHUJLD IRUQHFLGD
SDUD D DPRVWUD RX SDUD D UHIHUrQFLD GHSHQGHQGR GR SURFHVVR HQYROYLGR VHU

 $QiOLVH7pUPLFD'LIHUHQFLDO '7$ H&DORULPHWULD'LIHUHQFLDOGH9DUUHGXUD '6& 


HQGRWpUPLFR RX H[RWpUPLFR ,VWR WHP FRPR ILQDOLGDGH PDQWHU D DPRVWUD H D
UHIHUrQFLD FRP D PHVPD WHPSHUDWXUD 2XWUD GHILQLomR SDUD '6& HQFRQWUDGD QD
OLWHUDWXUD p D GH TXH QHVWD WpFQLFD D WHPSHUDWXUD GD DPRVWUD DFRPSDQKD D
WHPSHUDWXUD GD UHIHUrQFLD DWUDYpV GR JDQKR RX SHUGD GH FDORU FRQWURODGR SHOR
HTXLSDPHQWR2VGHWDOKHVRSHUDFLRQDLVGHSHQGHPGDFRQVWUXomRGHFDGDIDEULFDQWH
PDV HP WRGRV RV FDVRV DV WHPSHUDWXUDV GD DPRVWUD H GD UHIHUrQFLD VmR PDQWLGDV
LJXDLV2UHJLVWURGDFXUYDGH'6&pH[SUHVVRHPWHUPRVGHIOX[RGHFDORU PLOLZDWWV
P: YHUVXVWHPSHUDWXUD R& RXWHPSR PLQ 
(P '7$ R IOX[R GH FDORU G4GW p GHULYDGR GD PHGLGD GD GLIHUHQoD GH
WHPSHUDWXUDHQWUHXPPDWHULDOGHUHIHUrQFLDHDDPRVWUD8PDRXWUDGLIHUHQoDHQWUH
R'7$HR'6&pTXDQWRjIDL[DGHWHPSHUDWXUDGHRSHUDomRTXHGHXPPRGRJHUDO
YDULDGHDR&SDUDR'7$HGHDR&SDUDR'6&
$)LJXUDPRVWUDGRLVGLDJUDPDVGHEORFRXPSDUDR'7$HRXWURSDUDR'6&
QRV TXDLV p SRVVtYHO REVHUYDU DV SULQFLSDLV GLIHUHQoDV GH FRQVWUXomR GRV
HTXLSDPHQWRV

)LJXUD'LDJUDPDVGHEORFRVGH'7$H'6&

$OJXQV DXWRUHV WHQGHP D WUDWDU DV WpFQLFDV '7$ H '6& FRPR GXDV WpFQLFDV
GLVWLQWDV H LQGHSHQGHQWHV (QWUHWDQWR D OLWHUDWXUD EiVLFD GH DQiOLVH WpUPLFD
DSUHVHQWDDVHJXLQWHUHODomRHQWUHDVGXDVRPpWRGRGHDQiOLVHWpUPLFDGLIHUHQFLDO
'7$  DSOLFDGR j PHGLGD GH FDORU p GHQRPLQDGR FDORULPHWULD GLIHUHQFLDO GH
YDUUHGXUD '6& $VVLP'7$VHULDRWHUPRJOREDODEUDQJHQGRWRGDVDVWpFQLFDVGH

&DUDFWHUL]DomRGH3ROtPHURV  
DQiOLVH WpUPLFD GLIHUHQFLDO H '6& VHULD R WHUPR UHVHUYDGR SDUD R '7$ TXH IRUQHFH
LQIRUPDo}HVFDORULPpWULFDV
$ )LJXUD  PRVWUD XPD FXUYD GH '6& WtSLFD RQGH DVVLP FRPR R '7$ WUrV
WLSRV EiVLFRV GH WUDQVIRUPDo}HV SRGHP VHU GHWHFWDGRV WUDQVIRUPDo}HV
HQGRWpUPLFDV WUDQVIRUPDo}HV H[RWpUPLFDV H WUDQVLo}HV GH VHJXQGD RUGHP &RPR
H[HPSORGHWUDQVLomRGHVHJXQGDRUGHPSRGHVHUFLWDGDDWHPSHUDWXUDGHWUDQVLomR
YtWUHD 7J QD TXDO D HQWDOSLD QmR VRIUH YDULDomR PDV R FDORU HVSHFtILFR VRIUH XPD
PXGDQoDUHSHQWLQD

)LJXUD&XUYDGH'6&GHDPRVWUDGHSROL WHUHIWDODWRGHHWLOHQR  3(7 UHJLVWUDGDDR&PLQ

10.3.2 Aplicaes gerais do DSC


'HVWHPRGRHQWUHDVDSOLFDo}HVGR'6&SRGHPVHUFLWDGDV

determinao das temperaturas de transio em polmeros


SWUDQVLomRYtWUHD7J
SWHPSHUDWXUDGHFULVWDOL]DomR7F
SWHPSHUDWXUDGHIXVmR7P

medidas quantitativas
SFDORUHVSHFtILFR &S 
SFDORUGHIXVmR +I 

 $QiOLVH7pUPLFD'LIHUHQFLDO '7$ H&DORULPHWULD'LIHUHQFLDOGH9DUUHGXUD '6& 


SFDORUGHFULVWDOL]DomR +F 
SFDORUGHUHDomR +U 

10.3.3 Procedimento experimental


$H[HPSORGRTXHIRLIHLWRSDUDDWHUPRJUDYLPHWULDVHUiGHVFULWRDVHJXLUGHPRGR
JHQpULFRRSURFHGLPHQWRGHXPDDQiOLVHGH'6&FRPRREMHWLYRGHIDPLOLDUL]DUR
OHLWRU TXH QmR WHQKD DFHVVR D XP HTXLSDPHQWR D UHVSHLWR GH SHTXHQRV GHWDOKHV
RSHUDFLRQDLV 1R FDVR GH KDYHU XP HTXLSDPHQWR GLVSRQtYHO p LPSUHVFLQGtYHO D
OHLWXUD GR PDQXDO ([LVWHP GHWDOKHV RSHUDFLRQDLV TXH VH QmR IRUHP REVHUYDGRV
FRPSURPHWHUmR RV UHVXOWDGRV IRUQHFLGRV SHOR HTXLSDPHQWR H DWp PHVPR R VHX
IXQFLRQDPHQWR

Procedimento operacional:
S/LJDURHTXLSDPHQWR
S$MXVWDUDDWPRVIHUDQRFRPSDUWLPHQWRGDDPRVWUD3RGHVHUXVDGRYiFXR DWp
a[WRUU JiVLQHUWH QLWURJrQLR1 RXDLQGDDWPRVIHUDUHDWLYDRXFRUURVLYD
GLy[LGR GH HQ[RIUH 62  2 PRGR GH RSHUDomR PDLV FRPXP QD DQiOLVH GH
SROtPHURVpFRPIOX[RGHJiVLQHUWH QRUPDOPHQWH1 1DDQiOLVHGH'6&RIOX[R
GH1QmRLQIOXHQFLDRUHVXOWDGRGDVWHPSHUDWXUDVGHWUDQVLomRREVHUYDGDV
S(VFROKD GRV SDUkPHWURV QR SURFHVVDGRU GH GDGRV PLFURFRPSXWDGRU  
7HPSHUDWXUD LQLFLDO WHPSHUDWXUD ILQDO H YHORFLGDGH GH DTXHFLPHQWR RX
UHVIULDPHQWR 1R FDVR GH SURFHGLPHQWR LVRWpUPLFR HVWDEHOHFHU D WHPSHUDWXUD D
VHUIL[DGDHRWHPSRGDDQiOLVH
S2EWHQomR GD OLQKDEDVH  &RPR SRGH VHU REVHUYDGR QD )LJXUD  D 7J p
GHWHFWDGD SRU XPD VLPSOHV GHVFRQWLQXLGDGH QR IOX[R GH FDORU 3DUD VH WHU
VHJXUDQoD QHVWD LQWHUSUHWDomR p QHFHVViULR TXH VH WHQKD D FHUWH]D GH TXH R
HTXLSDPHQWR QmR DSUHVHQWH QHQKXP WLSR GH YDULDomR QD FXUYD TXDQGR QmR
RFRUUH WUDQVIRUPDomR DOJXPD QD DPRVWUD 3DUD WDQWR p UHDOL]DGD XPD DQiOLVH
XWLOL]DQGR GXDV FiSVXODV SRUWDDPRVWUDV  YD]LDV XPD QR FRPSDUWLPHQWR GD
DPRVWUDHRXWUDQRGDUHIHUrQFLD(VWHSURFHGLPHQWRGHYHUiIRUQHFHUXPJUiILFR
FRPXPDOLQKDSUDWLFDPHQWHUHWDWHQGHQGRDXPDSDUDOHODDRHL[RGDVDEFLVVDV
(VWDOLQKDpGHQRPLQDGDOLQKDEDVH

e LPSRUWDQWH LQIRUPDU TXH D FiSVXOD RX FDGLQKR RQGHDDPRVWUDpFRORFDGDp


YXOJDUPHQWHFRQKHFLGDSHORQRPHGHSDQHOLQKD
S&DOLEUDomR  2XWUR GHWDOKH LPSRUWDQWH p WHU FHUWH]D GH TXH D WHPSHUDWXUD QD
TXDORSLFRDSDUHFHUipUHDOPHQWHDWHPSHUDWXUDQDTXDODWUDQVIRUPDomRRFRUUH
HDWURFDGHFDORUHQYROYLGDpFRUUHWD$VVLPpQHFHVViULRFDOLEUDURLQVWUXPHQWR
XWLOL]DQGR XPD DPRVWUDSDGUmR $ DQiOLVH p UHDOL]DGD FRP R FRPSDUWLPHQWR GD

&DUDFWHUL]DomRGH3ROtPHURV  
UHIHUrQFLD FRQWHQGR D FiSVXOD YD]LD H R FRPSDUWLPHQWR GD DPRVWUD FRQWHQGR
RXWUDFiSVXODFRPDVXEVWkQFLDSDGUmR$7DEHODDSUHVHQWDDOJXQVSDGU}HV
TXHVmRXWLOL]DGRVSDUDFDOLEUDomRGHWHPSHUDWXUDGHIXVmRFULVWDOLQDHFDORUGH
IXVmR$HVFROKDGRSDGUmRDVHUXWLOL]DGRHVWiQRUPDOPHQWHUHODFLRQDGDjIDL[D
GHWHPSHUDWXUDGDVDQiOLVHVGHVHMDGDV8PDVXEVWkQFLDEDVWDQWHXWLOL]DGDFRPR
SDGUmRpRPHWDOtQGLR
7DEHOD3DGU}HVGHFDOLEUDomRSDUDDQiOLVHHP'6&

3DGU}HV 7P R&  +I FDOJ 


JXD  
%HQ]RIHQRQD  
1DIWDOHQR  
FLGREHQ]yLFR  
QGLR  
(VWDQKR  
&KXPER  
=LQFR  
$OXPtQLR  

S$QiOLVH GD DPRVWUD  $ DPRVWUD p SUHSDUDGD FRORFDQGRVH R PDWHULDO D VHU


H[DPLQDGR HP XPD FiSVXOD JHUDOPHQWH GH DOXPtQLR TXH p SURYLGD GH XPD
WDPSD $ DPRVWUD p SHVDGD H D VHJXLU D FiSVXOD p VHODGD HP XP GLVSRVLWLYR
HVSHFLDOSDUDHVWHILPGHQRPLQDGRGHSUHQVD2FRQWDWRHQWUHDVVXSHUItFLHVGR
PDWHULDOHDGDFiSVXODGHYHVHUPi[LPRXPDYH]TXHLVWRPHOKRUDDUHVROXomR
GRSLFRUHJLVWUDGR2VWLSRVGHDPRVWUDPDLVUHFRPHQGDGRVVmRGLVFRVILOPHVRX
JUmRVILQRV$SUHQVDVHODDFiSVXODPDVHODQmRILFDKHUPHWLFDPHQWHIHFKDGD

%DVLFDPHQWHH[LVWHPGRLVWLSRVGHFiSVXODVXPDSDUDDPRVWUDVOtTXLGDVHRXWUD
SDUD DPRVWUDV VyOLGDV 1R FDVR GH DPRVWUDV OtTXLGDV R IRUPDWR GD FiSVXOD p
GLIHUHQWHGRXVDGRSDUDPDWHULDLVVyOLGRV DDPRVWUDILFDPDLVKHUPpWLFD 
$VVLPpQHFHVViULRHVFROKHURWLSRGHFiSVXOD'HYHVHHQWmRSHVDUDDPRVWUDQD
FiSVXOD DGHTXDGD IHFKiOD H FRORFiOD QR FRPSDUWLPHQWR GD DPRVWUD 2 FRP
SDUWLPHQWR GD UHIHUrQFLD SURYDYHOPHQWH Mi HVWDUi FRP XPD FiSVXOD VHPHOKDQWH
YD]LD DPHVPDTXHIRLXWLOL]DGDSDUDDREWHQomRGDOLQKDEDVHHFDOLEUDomR 'LJLWDU
D PDVVD GD DPRVWUD QR FRPSXWDGRU H LQLFLDU D DQiOLVH 5HDOL]DU SHOR PHQRV GRLV
FLFORV GH DTXHFLPHQWRUHVIULDPHQWR LJXDLV *HUDOPHQWH R SULPHLUR UHJLVWUR p GHV
SUH]DGR$ILQDOLGDGHGHVWHSURFHGLPHQWRpHOLPLQDUDKLVWyULDWpUPLFDGRPDWHULDO
SROLPpULFRH[DPLQDGR(QWUHWDQWRFRPRVHUiGLVFXWLGRDGLDQWHFHUWRVSURFHVVRVGH

 $QiOLVH7pUPLFD'LIHUHQFLDO '7$ H&DORULPHWULD'LIHUHQFLDOGH9DUUHGXUD '6& 


WUDQVIRUPDomR VmR UHJLVWUDGRV VRPHQWH GXUDQWH R SULPHLUR FLFOR XP H[HPSOR p D
UHDomRGHUHWLFXODomRGHSROtPHURV FXUD 

10.3.4 Anlise da curva de DSC


'HSRVVHGDFXUYDGH'6&DVWUDQVLo}HVGHLQWHUHVVHSRGHPVHUREVHUYDGDV$VHJXLU
VHUmRGHVFULWRVDOJXQVPpWRGRVGHGHWHUPLQDomRGDWHPSHUDWXUDUHODFLRQDGDDHVVDV
WUDQVLo}HV&RPRH[HPSORYDPRVFLWDUDOHLWXUDGH7JH7P

10.3.4.1 Determinao da temperatura de fuso (Tm)


$7PSRGHVHUWRPDGDHPSRQWRVFRPRPRVWUDD)LJXUD D QRLQtFLRGRSLFR
E QRPi[LPRGRSLFRH F QRILPGRSLFR$VWHPSHUDWXUDVQRLQtFLRHQRILQDOGR
SLFR VmR GHWHUPLQDGDV QD LQWHUVHomR GRV SURORQJDPHQWRV 2 SRQWR D  GHQRWD D
IXVmRGRVSULPHLURVFULVWDLVRSRQWR E DIXVmRGDPDLRULDGRVFULVWDLVHRSRQWR F 
DWHPSHUDWXUDHPTXHRFRUUHDIXVmRGHWRGRVRVFULVWDLV

)LJXUD'HWHUPLQDomRGDWHPSHUDWXUDGHIXVmRFULVWDOLQD 7P GHXPDFXUYDGH'6&QRLQtFLRGDIXVmR
7 QRPi[LPRGRSLFR 7 QRILPGDIXVmR 7 

1HVWHSRQWRXPDPHVPDTXHVWmRpVHPSUHDERUGDGD

Qual o mtodo mais significativo?


1RFDVRGHWUDQVLo}HVGHSULPHLUDRUGHPFRPRIXVmRFULVWDOL]DomRHWFDHVFROKDGR
PpWRGR GHSHQGHUi GR HVWXGR TXH HVWi VHQGR IHLWR 6H R REMHWLYR GR HVWXGR IRU D
GHWHUPLQDomRGDWHPSHUDWXUDQDTXDORVFULVWDLVFRPHoDPDVHIXQGLUDWHPSHUDWXUD
GHYHVHUOLGDQRSRQWR D $OHLWXUDQRSRQWR E SRGHVHUXVDGDSDUDHVWDEHOHFHUD
WHPSHUDWXUD QD TXDO D PDLRULD GRV FULVWDLV VH IXQGHP $ OHLWXUD QR SRQWR F  p
DGRWDGDTXDQGRIRUGHLQWHUHVVHHVWDEHOHFHUDWHPSHUDWXUDFRUUHVSRQGHQWHjIXVmR
FRPSOHWDGRVFULVWDLV

&DUDFWHUL]DomRGH3ROtPHURV  
10.3.4.2 Determinao da temperatura de transio vtrea (Tg)
2YDORUGH7JWDPEpPSRGHVHUGHWHUPLQDGRSRUPpWRGRVGLVWLQWRVFRPRPRVWUDD
)LJXUD D QRLQtFLRGDWUDQVLomR7 E QDPHLDDOWXUDGRVSURORQJDPHQWRV7
H F QRSRQWRGHLQIOH[mRGDFXUYD72LQtFLRGDWUDQVLomRpWRPDGRDSDUWLUGD
LQWHUVHomR GRV SURORQJDPHQWRV GD GHVFRQWLQXLGDGH $ PHLD DOWXUD GRV
SURORQJDPHQWRVGL]UHVSHLWRDRSURORQJDPHQWRGDVOLQKDVWDQJHQWHVjFXUYDDQWHVH
DSyV D WUDQVLomR WUDoDQGRVH XPD SHUSHQGLFXODU D HVWHV SURORQJDPHQWRV D TXDO p
FRUWDGD DR PHLR SHOD FXUYD GH '6& 2 SRQWR GH LQIOH[mR p DTXHOH QR TXDO D
GHVFRQWLQXLGDGH p Pi[LPD 1DV FXUYDV j HVTXHUGD GD )LJXUD  REVHUYDVH TXH
SUDWLFDPHQWHQmRKiYDULDomRQRYDORUGDWHPSHUDWXUDWRPDGDSHORVWUrVPpWRGRV
GLVWLQWRV 3RUpP QRUPDOPHQWH RFRUUH XPD YDULDomR QD WHPSHUDWXUD GH WUDQVLomR
HPIXQomRGRPpWRGRGHGHWHUPLQDomRXWLOL]DGRFRPRLOXVWUDPDVFXUYDVjGLUHLWD
GD)LJXUD,VWRpGHSHQGHQGRGRPpWRGRXWLOL]DGRRYDORUREWLGRSDUD7JVHUi
GLIHUHQWH

)LJXUD0pWRGRVGHGHWHUPLQDomRGH7JHPFXUYDVGH'6&

 $QiOLVH7pUPLFD'LIHUHQFLDO '7$ H&DORULPHWULD'LIHUHQFLDOGH9DUUHGXUD '6& 


6HDPHGLGDTXHHVWiVHQGRIHLWDpGH7JpPDLVDFRQVHOKiYHOXVDURPpWRGR E 
SRUTXHSHUPLWHPHGLURXWURVSDUkPHWURVFRPRDODUJXUDGDWUDQVLomRYtWUHD 7J H
D YDULDomR GD FDSDFLGDGH FDORUtILFD &S  (VWHV SDUkPHWURV VmR ~WHLV QR FDVR GR
HVWXGR GH FRSROtPHURV H PLVWXUDV GH SROtPHURV e R PpWRGR PDLV DFHLWR H HVWi
GHVFULWRQD$670'
$VVLP WDQWR SDUD 7P TXDQWR SDUD 7J R YDORU GD WHPSHUDWXUD GHSHQGHUi GR
PpWRGRGHGHWHUPLQDomRXWLOL]DGR,VVRH[SOLFDDLPSRUWkQFLDGHVHXVDUVHPSUHR
PHVPRPpWRGRHPHVWXGRVFRPSDUDWLYRVSRGHQGRDLQGDFLWDURPpWRGRXWLOL]DGR
TXDQGRQHFHVViULR

10.3.4.3 Determinao do calor especfico (Cp)


$GHWHUPLQDomRGRFDORUHVSHFtILFRpRXWURWLSRGHPHGLGDTXHSRGHVHUREWLGDSRU
PHLR GD FXUYD GH '6& 2 FDORU HVSHFtILFR p ~WLO SDUD DYDOLDU DV SURSULHGDGHV GRV
VLVWHPDV IRUPDGRV SRU SROtPHURV 4XDQGR D DPRVWUD p VXEPHWLGD D XPD YDULDomR
OLQHDU GD WHPSHUDWXUD D YHORFLGDGH FRP TXH R FDORU IOXL GHQWUR GD DPRVWUD p
SURSRUFLRQDODRVHXFDORUHVSHFtILFR&SQDTXHOHLQVWDQWH2FDORUHVSHFtILFRGHXPD
DPRVWUD GHSHQGH GD WHPSHUDWXUD (OH SRGH VHU GHWHUPLQDGR SRU PHLR GD
FRPSDUDomR HQWUH DV YDULDo}HV GR IOX[R GH FDORU FRP D WHPSHUDWXUD PHGLGD SDUD
HVVHPDWHULDOHSDUDXPDVXEVWkQFLDSDGUmR
2SURFHGLPHQWRpVLPSOHVHSRGHVHUGHVFULWRGDVHJXLQWHIRUPD
SFRORFDU QR HTXLSDPHQWR GXDV FiSVXODV GH DOXPtQLR YD]LDV XPD QR
FRPSDUWLPHQWRGDDPRVWUDHDRXWUDQDUHIHUrQFLD
SVHOHFLRQDUDIDL[DGHWHPSHUDWXUDHPTXHVHUiPHGLGRRFDORUHVSHFtILFR
SUHJLVWUDU XPD OLQKDEDVH QD WHPSHUDWXUD PDLV EDL[D DXPHQWDU D WHPSHUDWXUD
DWpROLPLWHGDIDL[DSUHYLDPHQWHVHOHFLRQDGDHUHJLVWUDUDOLQKDEDVHLVRWpUPLFD
QDWHPSHUDWXUDPDLVDOWD2UHJLVWURGHVHMDGRFRUUHVSRQGHjOLQKD D GD)LJXUD

SUHSHWLU R SURFHGLPHQWR SDUD XPD PDVVD FRQKHFLGD GH XPD VXEVWkQFLD SDGUmR
FRPRSRUH[HPSORDVDILUD y[LGRGHDOXPtQLR 
SUHSHWLURSURFHGLPHQWRSDUDXPDPDVVDFRQKHFLGDGDDPRVWUD
SFDOFXODURFDORUHVSHFtILFRSRUPHLRGDUHODomR
Cp a y a m s
= .
Cp s y s m a (10.1)
RQGH&SpRFDORUHVSHFtILFRHPFDOJ\pRGHVORFDPHQWRGDSHQDGRUHJLVWUDGRUD
XPD GHWHUPLQDGD WHPSHUDWXUD H P p D PDVVD 2V tQGLFHV D H V FRUUHVSRQGHP j
DPRVWUDHjVDILUD2VYDORUHVGRFDORUHVSHFtILFRGDVDILUDVmREHPHVWDEHOHFLGRVH
HVWmR WDEHODGRV $VVLP FRP DSHQDV GXDV OHLWXUDV GH G+GW IHLWDV D XPD PHVPD

&DUDFWHUL]DomRGH3ROtPHURV  
WHPSHUDWXUDSDUDDDPRVWUDHSDUDRSDGUmRSRGHVHGHWHUPLQDUDUD]mRHQWUHRV
UHVSHFWLYRV&SV
$SDUHOKRVPDLVPRGHUQRVGLVS}HPGHSURJUDPDVHVSHFtILFRVSDUDFiOFXORGH&S
RVTXDLVVmREDVHDGRVQDGHVFULomRDFLPD

)LJXUD'HWHUPLQDomRGRFDORUHVSHFtILFRSRU'6&

10.3.5 Fatores que influenciam o resultado da anlise


8PDREVHUYDomRLPSRUWDQWHDVHUIHLWDVREUHDDQiOLVHGH'7$'6&pTXHDH[HPSOR
GR RFRUUH QD 7*$RYDORUGDWHPSHUDWXUDQDTXDORFRUUHDWUDQVIRUPDomRREWLGD
SHOD FXUYD GH DQiOLVH WpUPLFD H D UHVROXomR GD DQiOLVH GHSHQGHP GH IDWRUHV
LQVWUXPHQWDLVHGHIDWRUHVDVVRFLDGRVjDPRVWUDHjUHIHUrQFLD
2V IDWRUHV LQVWUXPHQWDLV PDLV VLJQLILFDWLYRV VmR D YHORFLGDGH GH YDULDomR GH
WHPSHUDWXUD R GLVSRVLWLYR TXH FRQWpP D DPRVWUD R VHQVRU GH WHPSHUDWXUD H D
IRUPD GH UHJLVWUR 3RU H[HPSOR VH D YDULDomR GD WHPSHUDWXUD GH DTXHFLPHQWR IRU
UiSLGD YHORFLGDGH DOWD  SRGH KDYHU R GHVORFDPHQWR GR SLFR GH IXVmR SDUD
WHPSHUDWXUDVPDLVDOWDVHXPDXPHQWRQDiUHDVREDFXUYDGH'7$2VGLVSRVLWLYRV
XVDGRVFRPRFRPSDUWLPHQWRGHDPRVWUDSRGHPVHUFRQVWUXtGRVFRPGLYHUVRVWLSRV
GH PDWHULDO FRPR FREUH SUDWD DOXPtQLR H FHUkPLFD (VWHV PDWHULDLV WrP
FRQGXWLYLGDGHWpUPLFDHFDSDFLGDGHFDORUtILFDGLIHUHQWHVHSRUWDQWRSRGHPDIHWDUD
IRUPD GD FXUYD H D PDJQLWXGH GR HYHQWR WpUPLFR 4XDQWR DRV VHQVRUHV GH
WHPSHUDWXUDDVXDLQIOXrQFLDpPDLRUQDVFXUYDVGH'7$$IRUPDGHUHJLVWURJHUD
FXUYDVGLIHUHQWHVVHIRUHPXVDGRVHVTXHPDVGHUHJLVWURGLIHUHQWHV3RUH[HPSORD
FXUYD7YHUVXVWHPSHUDWXUDpGLIHUHQWHGDFXUYD7YHUVXVWHPSR

 $QiOLVH7pUPLFD'LIHUHQFLDO '7$ H&DORULPHWULD'LIHUHQFLDOGH9DUUHGXUD '6& 


$ DPRVWUD SRGH LQIOXHQFLDU R UHVXOWDGR SHOR VHX WDPDQKR SHOD IRUPD GH
HPSDFRWDPHQWRSHORWDPDQKRHGLVWULEXLomRGDVSDUWtFXODVTXHDFRQVWLWXHPSHOD
DWPRVIHUDHPTXHDDQiOLVHpUHDOL]DGDHSHORWUDWDPHQWRSUpYLR
2 HIHLWR GD UHIHUrQFLD p PDLRU QR FDVR GR '7$ HP TXH Ki D QHFHVVLGDGH GD
DQiOLVH VHU UHDOL]DGD FRP PDWHULDO LQHUWH HP WRGD D IDL[D GH WHPSHUDWXUD XVDGD H
FRPFDUDFWHUtVWLFDVWpUPLFDVHIDL[DGHWDPDQKRGHSDUWtFXODVSUy[LPDVGDDPRVWUD
2'6&XWLOL]DFRPRUHIHUrQFLDXPDFiSVXODYD]LD
$ LQIOXrQFLD GD YHORFLGDGH GH YDULDomR GD WHPSHUDWXUD HVFROKLGD SRGH VHU
LOXVWUDGDFRPPDLRUGHWDOKH$)LJXUDPRVWUDRVYDORUHVGH7PHQFRQWUDGRVHP
FXUYDV GH '6& SDUD DQiOLVHV GH XPD DPRVWUD GH 3(7 UHDOL]DGDV D GLIHUHQWHV
YHORFLGDGHV GH DTXHFLPHQWR 3RGHVH REVHUYDU TXH D WHPSHUDWXUD GH IXVmR
GHWHUPLQDGD SHODV FXUYDV GH '6& DXPHQWD FRP R DXPHQWR GD YHORFLGDGH GH
DTXHFLPHQWR ,VWR RFRUUH SRUTXH D DPRVWUD QmR SHUFHEH HVVH DXPHQWR WmR
UDSLGDPHQWH1RWHTXHQDUHWDFRUUHVSRQGHQWHjDPRVWUDVREDIRUPDGHJUkQXORR
HIHLWR p PDLV HYLGHQWH SRLV R FDORU VH GLVWULEXL SRU WRGD D DPRVWUD FRP PDLRU
GLILFXOGDGHTXHQDDPRVWUDVREDIRUPDGHSy

)LJXUD'HSHQGrQFLDGD7PFRPDYHORFLGDGHGHDTXHFLPHQWRSDUDDPRVWUDVGH3(7VREDIRUPDGHSyH
JUkQXOR

$)LJXUDLOXVWUDDLQIOXrQFLDGDYHORFLGDGHGHDTXHFLPHQWRGDDQiOLVHVREUH
D UHVROXomR GR SLFR 8P H[HPSOR p D PLVWXUD GH GXDV DPRVWUDV GH SROtPHURV
VHPLFULVWDOLQRV FXMDV WHPSHUDWXUDV GH IXVmR HVWHMDP EHP SUy[LPDV $R UHDOL]DU D
DQiOLVHVRPHQWHXPSLFRGHIXVmRpUHJLVWUDGR(VWHUHVXOWDGRGiDLPSUHVVmRTXH

&DUDFWHUL]DomRGH3ROtPHURV  
H[LVWHDSHQDVXPDUHJLmRFULVWDOLQDTXDQGRVHVDEHTXHVHWUDWDGHGXDVDPRVWUDV
VREDIRUPDGHSyFRORFDGDVHPFRQWDWRQDFiSVXOD

possvel que cadeias dos dois tipos de polmeros possam apresentar


apenas um tipo de cristal?
$UHVSRVWDpVLPSOHVLVVRQmRRFRUUH$RSUHSDUDURXWUDDPRVWUDGDPHVPDPLVWXUD
FRPRPHVPRSURFHGLPHQWRHUHDOL]DUDDQiOLVHDXPDYHORFLGDGHGHDTXHFLPHQWR
PDLVOHQWDVmRREVHUYDGRVGRLVSLFRVFDGDXPUHODWLYRjIXVmRGDUHJLmRFULVWDOLQD
GHFDGDSROtPHUR

Por que isto ocorre ?


5HDOL]DQGRVHDDQiOLVHDXPDYHORFLGDGHGHDTXHFLPHQWRVXILFLHQWHPHQWHEDL[DDR
DWLQJLU D WHPSHUDWXUD GH IXVmR GD UHJLmR FULVWDOLQD TXH IXQGH D PDLV EDL[D
WHPSHUDWXUDRVFULVWDLVYmRFRPHoDUDIXQGLUHDJUDQGHPDLRULDGRVFULVWDLVMiWHUi
IXQGLGRDQWHVTXHDWHPSHUDWXUDGHDQiOLVHVHMDVXILFLHQWHSDUDLQLFLDUDIXVmRGRV
FULVWDLVGDRXWUDDPRVWUDGHSROtPHUR3RURXWURODGRUHDOL]DQGRVHDDQiOLVHDXPD
YHORFLGDGH GH DTXHFLPHQWR UHODWLYDPHQWH UiSLGD RV FULVWDLV GH XPD DPRVWUD
FRPHoDPDVHIXQGLUHUDSLGDPHQWHDWHPSHUDWXUDGRFRPSDUWLPHQWRGDDPRVWUDMi
p VXILFLHQWH SDUD LQLFLDU D IXVmR GRV FULVWDLV GD RXWUD DPRVWUD MXQWDPHQWH FRP D
IXVmRGDPDLRULDGRVFULVWDLVGDSULPHLUDDPRVWUD(VWHIHQ{PHQRQDFXUYDGH'6&
DSDUHFHFRPRXP~QLFRSLFR
eLPSRUWDQWHVDOLHQWDUTXHDSHVDUGDUHVROXomRGDDQiOLVHVHUPHOKRUDGDDXPD
YHORFLGDGH GH DTXHFLPHQWR PDLV OHQWD LVWR QmR VLJQLILFD TXH VHPSUH VHUi SRVVtYHO
REWHU SLFRV VHSDUDGRV FRPR IRL FLWDGR DFLPD &DVR DV WUDQVLo}HV VHMDP PXLWR
SUy[LPDV H[LVWHP RXWUDV OLPLWDo}HV FRPR D IDL[D GD WUDQVLomR ODUJXUD GR SLFR 
JUDX GH FULVWDOLQLGDGH KLVWyULD WpUPLFD WDPDQKR GD DPRVWUD SUHFLVmR GR
HTXLSDPHQWRHWF

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)LJXUD$QiOLVHGH'6&GHDPRVWUDVGHSROLHWLOHQRUHDOL]DGDVDGLIHUHQWHVYHORFLGDGHVGHDTXHFLPHQWR

&RPR D YHORFLGDGH GH DTXHFLPHQWR LQIOXHQFLD QR YDORU GD WHPSHUDWXUD


HQFRQWUDGD SDUD D WUDQVIRUPDomR D QRUPD $670 ' HVSHFLILFD FRPR
YHORFLGDGHV GH DTXHFLPHQWR DGHTXDGDV R&PLQ SDUD GHWHUPLQDomR GH 7P H
R&PLQ SDUD D GHWHUPLQDomR GH 7J e FODUR TXH D DQiOLVH SRGH VHU IHLWD QD
YHORFLGDGHGHDTXHFLPHQWRTXHVHGHVHMDURXTXHIRUHPDVPDLVFRQYHQLHQWHVPDV
HP QtYHO GH FRPSDUDomR FRP UHVXOWDGRV SXEOLFDGRV QD OLWHUDWXUD UHFRPHQGDVH
VHJXLUDQRUPD$670

10.3.6 Relao entre entalpia e rea do pico


$WpDTXLDDQiOLVHGDFXUYDGH'6&VHUHVWULQJLXSULRULWDULDPHQWHjGHWHUPLQDomRGD
WHPSHUDWXUD QD TXDO D DPRVWUD VRIUH XPD WUDQVIRUPDomR 0DV FRPR IRL GLWR QR
LQtFLR GR FDStWXOR HVVDV LQIRUPDo}HV SRGHP VHU REWLGDV WDPEpP QR '7$ H TXH R

&DUDFWHUL]DomRGH3ROtPHURV  
'6& IRUQHFH DLQGD LQIRUPDo}HV D UHVSHLWR GD TXDQWLGDGH GH FDORU HQYROYLGR QD
WUDQVIRUPDomR(VWDTXDQWLGDGHGHFDORUHVWDULDGLUHWDPHQWHUHODFLRQDGDjiUHDGR
SLFRJHUDGRSHODUHIHULGDWUDQVIRUPDomR3RUH[HPSORDiUHDGHXPSLFRGHIXVmRp
SURSRUFLRQDODR+IGDDPRVWUDHjTXDQWLGDGHGHDPRVWUDFRORFDGDQDFiSVXOD1mR
VH GHYH HVTXHFHU TXH VH D DPRVWUD VRIUH XPD WUDQVIRUPDomR HQGRWpUPLFD TXDQWR
PDLRU IRU D TXDQWLGDGH GH DPRVWUD DQDOLVDGD PDLV FDORU VHUi DEVRUYLGR GXUDQWH D
WUDQVIRUPDomR $VVLP UHSUHVHQWDQGR D PDVVD GD DPRVWUD SRU P D YDULDomR GH
HQWDOSLDGHIXVmRSRU+IHDiUHDGRSLFRSRU$SRGHVHWHUDUHODomR
m. Hf = K.A (10.2)
RQGH.pDFRQVWDQWHGHSURSRUFLRQDOLGDGHDTXDOSRGHVHUGHWHUPLQDGDFRPRXVR
GHXPDDPRVWUDSDGUmRFXMRYDORUGH+IHQFRQWUDVHWDEHODGR8PDYH]WHQGRVLGR
FDOFXODGR R YDORU GH . R +I GH TXDOTXHU DPRVWUD SRGH VHU GHWHUPLQDGR
FRQKHFHQGRVH D TXDQWLGDGH GH DPRVWUD FRORFDGD QD FiSVXOD H D iUHD GR SLFR
FRUUHVSRQGHQWH
1D YHUGDGH LQVWUXPHQWRV HTXLSDGRV FRP FRPSXWDGRU IRUQHFHP GLUHWDPHQWH R
YDORU GH +I PDV p FRQYHQLHQWH OHPEUDU TXH HVVH YDORU QmR VXUJH GR QDGD R
FRPSXWDGRUHVWiDSHQDVID]HQGRRVFiOFXORVPRVWUDGRVDFLPD

10.3.7 Processos fsicos e qumicos que podem ser detectados por DSC
$7DEHODLOXVWUDDQDWXUH]DGDVWUDQVLo}HVPDLVXVXDLVGDVDSOLFDo}HVJHUDLVTXH
SRGHPVHUXWLOL]DGDVHPVLVWHPDVSROLPpULFRV

10.3.8 Exemplos de aplicaes


'HQWUHDVLQ~PHUDVDSOLFDo}HVH[LVWHQWHVSDUDHVWDVWpFQLFDVSRGHPVHUGHVWDFDGDV
DVVHJXLQWHV
SUHDo}HVGHGHFRPSRVLomR
SGLDJUDPDVGHIDVH
SFLQpWLFDGHUHDomR
SUHDo}HVGHGHVLGUDWDomR
SFDORUGHDGVRUomR
SFDORUGHUHDomRHSROLPHUL]DomR
SFDORUGHFULVWDOL]DomRIXVmRHVXEOLPDomR
SGHWHUPLQDomRGHSXUH]D
SHVWDELOLGDGHWpUPLFDHUHVLVWrQFLDjR[LGDomR
SGHWHUPLQDomRGHWUDQVLomRYtWUHD
SGHWHUPLQDomRGHFDORUHVSHFtILFR
SGHWHUPLQDomRGHJUDXGHFULVWDOLQLGDGH
SFLQpWLFDGHFULVWDOL]DomR

 $QiOLVH7pUPLFD'LIHUHQFLDO '7$ H&DORULPHWULD'LIHUHQFLDOGH9DUUHGXUD '6& 


7DEHOD7UDQVLo}HVUHODFLRQDGDVDRVSURFHVVRVItVLFRVHTXtPLFRVTXHRFRUUHPGXUDQWHRDTXHFLPHQWR

7UDQVLomR
3URFHVVR
(QGRWpUPLFD ([RWpUPLFD
$EVRUomR ; 
$GVRUomR  ;
&ULVWDOL]DomR  ;
'HVVRUomR ; 
)XVmR ; 
6XEOLPDomR ; 
)tVLFR 7UDQVLomRFULVWDOLQD ; ;
7UDQVLomROtTXLGRFULVWDOLQD ; 
7UDQVLomRGHSRQWRGH&XULH ; 
7UDQVLomRGHFDSDFLGDGH
$OWHUDomRGHOLQKDEDVH
FDORUtILFD
7UDQVLomRYtWUHD $OWHUDomRGHOLQKDEDVH
9DSRUL]DomR ; 
&RPEXVWmR  ;
'HFRPSRVLomR ; ;
'HJUDGDomRR[LGDWLYD  ;
'HVLGUDWDomR ; 
2[LGDomRHPDWPRVIHUD 
;
JDVRVD
3ROLPHUL]DomR  ;
4XtPLFR
3UpFXUD  ;
5HDomRFDWDOtWLFD  ;
5HDomRQRHVWDGRVyOLGR ; ;
5HDomRUHGR[ ; ;
5HGXomRHPDWPRVIHUD 
;
JDVRVD
6RUomRTXtPLFD  ;

$ )LJXUD  DSUHVHQWD DV LQIRUPDo}HV WtSLFDV IRUQHFLGDV SHOR '6& SDUD
DPRVWUDVGHSROtPHURV

&DUDFWHUL]DomRGH3ROtPHURV  
)LJXUD'LDJUDPDHVTXHPiWLFRGDVLQIRUPDo}HVWtSLFDVIRUQHFLGDVSHOR'6&SDUDDPRVWUDVGH
SROtPHURV

(VWH GLDJUDPD PRVWUD PDLV XPD YH] R FDUiWHU H[RWpUPLFR GD 7F H GD
YXOFDQL]DomR H D QDWXUH]D HQGRWpUPLFD GD 7P e LPSRUWDQWH PHQFLRQDU TXH R
SURFHVVRGHGHJUDGDomRSRGHVHUHQGRRXH[RWpUPLFRGHSHQGHQGRGREDODQoRJOREDO
GH DEVRUomR H OLEHUDomR GH FDORU GDV UHDo}HV TXtPLFDV TXH RFRUUHP GXUDQWH HVWH
SURFHVVRGHWUDQVIRUPDomR
6HUmR DSUHVHQWDGRV D VHJXLU FRP PDLRUHV GHWDOKHV DOJXQV H[HPSORV GH
DSOLFDomR

10.3.8.1 Estabilidade trmica


$ HVWDELOLGDGH WpUPLFD GH SROtPHURV SRGH VHU HVWXGDGD SRU '6& $ )LJXUD 
PRVWUD FXUYDV GH '6& GR SROL PHWDFULODWR GH PHWLOD  300$  H FRSROtPHURV
JUDIWL]DGRV j EDVH GH 300$ H SROLy[LGRV QXP SURJUDPD GH DTXHFLPHQWR (VWDV
DPRVWUDV VmR DPRUIDV H VXDV 7JV SRGHP VHU REVHUYDGDV D XPD WHPSHUDWXUD HP
WRUQR GH R& 1mR Ki SLFR UHODWLYR j 7P SRLV DV DPRVWUDV VmR DPRUIDV &RP R
DXPHQWRGDWHPSHUDWXUDSRGHVHUREVHUYDGRRSURFHVVRGHGHJUDGDomRWpUPLFDGDV
DPRVWUDV 2 300$ DSUHVHQWD XP SLFR HP WRUQR GH R& LQGLFDQGR TXH VHX
SURFHVVR GH GHJUDGDomR RFRUUH HP XP ~QLFR HVWiJLR (VWDV REVHUYDo}HV HVWmR GH
DFRUGRFRPDDQiOLVHGDPHVPDDPRVWUDGH300$UHDOL]DGDSRUWHUPRJUDYLPHWULD
)LJXUD $OpPGLVVRDWUDYpVGDDQiOLVHGH'6&REWpPVHDLQIRUPDomRTXDQWR
DR FDUiWHU HQGRWpUPLFR GR SURFHVVR GH GHJUDGDomR GR 300$ $V RXWUDV GXDV

 $QiOLVH7pUPLFD'LIHUHQFLDO '7$ H&DORULPHWULD'LIHUHQFLDOGH9DUUHGXUD '6& 


DPRVWUDVGHFRSROtPHURJUDIWL]DGRDSUHVHQWDPGRLVHVWiJLRVPDLVVLJQLILFDWLYRVGH
GHFRPSRVLomRWDPEpPFRPSURFHVVRJOREDOHQGRWpUPLFR
8PGHWDOKHSUiWLFRTXHSRGHVHUPHQFLRQDGRDTXLpRIDWRGHTXHHPJHUDOSDUD
HVWXGR GH GHJUDGDomR WpUPLFD HP '6& XWLOL]DVH D FiSVXOD VHP WDPSD D ILP GH
HYLWDU TXH RV SURGXWRV YROiWHLV SUHVVLRQHP R UHFLSLHQWH TXH SURPRYH D SHUGD GD
WDPSDHGHDOJXPPDWHULDODLQGDQmRYRODWLOL]DGR

)LJXUD&XUYDVGH'6&GH300$HFRSROtPHURVJUDIWL]DGRVGH300$FRPSROL y[LGRGHHWLOHQREy[LGR
GHSURSLOHQR  &23H&23WHRUHVYDULDGRVGHFDGHLDJUDIWL]DGD 

10.3.8.2 Influncia do peso molecular sobre a Tg


2 HIHLWR GR SHVR PROHFXODU PDVVD PRODU  VREUH D 7J SRGH VHU HVWXGDGR SRU '6&
$PRVWUDVGHGLIHUHQWHVSHVRVPROHFXODUHVVmRFRORFDGDVHPGLYHUVDVFiSVXODVHVmR
UHDOL]DGDV DQiOLVHV GH FDGD XPD GHVVDV DPRVWUDV GHWHUPLQDQGRVH D 7J FRPR
PHQFLRQDGRDQWHULRUPHQWH&RQVWUXLQGRVHXPJUiILFRGHYDORUGH7JHQFRQWUDGRQD
FXUYDGH'6&HPIXQomRGRSHVRPROHFXODUGDDPRVWUDDQDOLVDGDREWpPVHDFXUYD
LOXVWUDGD QD )LJXUD  $ 7J DSUHVHQWD XPD WHQGrQFLD GH DXPHQWDU FRP R
DXPHQWR GR SHVR PROHFXODU WRUQDQGRVH FRQVWDQWH D SDUWLU GH GHWHUPLQDGR YDORU
(VWHFRPSRUWDPHQWRVHUHSHWHSDUDDPDLRULDGRVSROtPHURVHRYDORUOLPLWHGHSHVR
PROHFXODU QR TXDO D 7J VH PDQWpP FRQVWDQWH p IXQomR GD HVWUXWXUD TXtPLFD GR
SROtPHUR
4XDQWRPHQRUIRURSHVRPROHFXODUPDLRUVHUiRQ~PHURUHODWLYRGHWHUPLQDLV
GH FDGHLD RV TXDLV HVWmR PDLV OLYUHV SDUD VH PRYLPHQWDU TXH RV VHJPHQWRV

&DUDFWHUL]DomRGH3ROtPHURV  
SRVLFLRQDGRV QR PHLR GD FDGHLD H WDPEpP PHQRU R Q~PHUR GH HPDUDQKDPHQWRV
IRUPDGRVSHODVFDGHLDVRVTXDLVGLILFXOWDPRPRYLPHQWRPROHFXODU

)LJXUD9DULDomRGD7JHPIXQomRGRSHVRPROHFXODU

8PDH[FHomRDHVWHFRPSRUWDPHQWRRFRUUHSDUDRSROL y[LGRGHHWLOHQR  3(2 $


)LJXUDPRVWUDRFRPSRUWDPHQWRGDFXUYDGH7JYHUVXVSHVRPROHFXODUSDUDR
3(2 DQWHV GH D 7J DWLQJLU XP YDORU FRQVWDQWH (VWH HVWXGR FRP 3(2 p GH JUDQGH
LPSRUWkQFLDXPDYH]TXHGLYHUVRVSURGXWRVjEDVHGH3(2GHEDL[RSHVRPROHFXODU
VmRFRPHUFLDOL]DGRVHXWLOL]DGRVHPGHVHQYROYLPHQWRGHSHVTXLVDV

)LJXUD9DULDomRGD7JHPIXQomRGRSHVRPROHFXODUGHDPRVWUDVGHSROL y[LGRGHHWLOHQR 

 $QiOLVH7pUPLFD'LIHUHQFLDO '7$ H&DORULPHWULD'LIHUHQFLDOGH9DUUHGXUD '6& 


10.3.8.3 Variao de Tg em funo da adio de um plastificante
$LQIOXrQFLDGDDGLomRGHSODVWLILFDQWHVREUHD7JGHXPPDWHULDOSROLPpULFRWDPEpP
SRGHVHUHVWXGDGDGHPRGRVHPHOKDQWHDRH[HPSORDQWHULRU$PRVWUDVFRPWHRUHV
GH SODVWLILFDQWH YDULDGRV VmR SUHSDUDGDV H DQDOLVDGDV LQGLYLGXDOPHQWH 3DUD FDGD
DPRVWUD REWpPVH XPD FXUYD GH '6& H XP YDORU GH 7J p GHWHUPLQDGR &RP HVWHV
UHVXOWDGRV p SRVVtYHO FRQVWUXLU XP JUiILFR GH 7J YHUVXV WHRU GH SODVWLILFDQWH QD
DPRVWUD &RPR LOXVWUD D )LJXUD  R SODVWLILFDQWH DWXD UHGX]LQGR D 7J GR
PDWHULDO4XDQWRPDLRUIRURWHRUGHSODVWLILFDQWHPHQRUVHUiRYDORUGD7JREWLGD2
SODVWLILFDQWH VXEVWkQFLD GH SHVR PROHFXODU PDLV EDL[R DX[LOLD QR PRYLPHQWR GDV
FDGHLDVGHSROtPHUR

)LJXUD9DULDomRGD7JHPIXQomRGRWHRUGHSODVWLILFDQWHHPXPDDPRVWUDGHSROtPHUR

10.3.8.4 Estudo de miscibilidade em polmeros


8PGRVFULWpULRVDGRWDGRVSDUDRHVWXGRGHPLVFLELOLGDGHHPVLVWHPDVSROLPpULFRV
EDVHLDVH QR IDWR GD PLVWXUD DSUHVHQWDU VRPHQWH XPD RX PDLV GH XPD 7J 'HVWH
PRGR R '6& p XP LQVWUXPHQWR EDVWDQWH ~WLO &RPR HVWH FULWpULR p EDVHDGR QD
YDULDomR GD WHPSHUDWXUD GH WUDQVLomR YtWUHD GR VLVWHPD WUDWDVH GH REVHUYDU R
HVWDGRDPRUIRGRPDWHULDO
&RQVLGHUDQGRVHXPSROtPHUR$FRPGHWHUPLQDGRYDORUGH7JHXPSROtPHUR%
FRPRXWURYDORUGH7J )LJXUD DRPLVWXUDUHVVHVGRLVSROtPHURVQDSURSRUomR
 HVWHV SRGHP IRUPDU XPD PLVWXUD LPLVFtYHO SDUFLDOPHQWH PLVFtYHO RX

&DUDFWHUL]DomRGH3ROtPHURV  
PLVFtYHO &DVR HVVHV SROtPHURV IRUPHP XPD PLVWXUD LPLVFtYHO VXDV FDGHLDV QmR
LQWHUDJHPHQWUHVLHVmRIRUPDGRVGRPtQLRVVHSDUDGRV,VWRVLJQLILFDTXHDVFDGHLDV
GRSROtPHUR$YmRDGTXLULUPRELOLGDGHQDPHVPDWHPSHUDWXUDUHJLVWUDGDFRPRVH
HVWLYHVVHP VR]LQKDV VHP VRIUHU D LQWHUIHUrQFLD GR SROtPHUR % 2 PHVPR DFRQWHFH
SDUD DV FDGHLDV GR SROtPHUR % 1HVWH FDVR VmR REVHUYDGDV GXDV 7JV QDV PHVPDV
WHPSHUDWXUDVGDV7JVGRVKRPRSROtPHURV$H%SXURV
8PD RXWUD SRVVLELOLGDGH p GH DV FDGHLDV GRV SROtPHURV $ H % WHUHP DOJXPD
DILQLGDGH HQWUH VL GH PRGR TXH H[LVWHP GRPtQLRV GH $ H % FRP DOJXPD
LQWHUSHQHWUDomR GH FDGHLD GH $ QRV GRPtQLRV GH % H YLFHYHUVD $ SUHVHQoD GH
FDGHLDV GH % TXH DGTXLUHP PRELOLGDGH D XPD WHPSHUDWXUD PDLV HOHYDGD  QRV
GRPtQLRVGH$LUiGLILFXOWDUDPRELOLGDGHGHVWDVFDGHLDVHOHYDQGRVXD7J3RURXWUR
ODGRDSUHVHQoDGHFDGHLDVGH$MiFRPPRELOLGDGHQRVGRPtQLRVGH%LUiIDFLOLWDUD
PRELOLGDGHGHVWH~OWLPRUHGX]LQGRVXD7J2UHVXOWDGRGLVVRpDREVHUYDomRGHGXDV
7JV HP WHPSHUDWXUDV VLWXDGDV HQWUH RV YDORUHV GH 7J GRV KRPRSROtPHURV $ H %
SXURV
8PDWHUFHLUDSRVVLELOLGDGHpGHTXHRFRUUDFRPSOHWDLQWHUDomRHQWUHDVFDGHLDV
GRV SROtPHURV $ H % 6XDV FDGHLDV VH LQWHUSHQHWUDP FRPR VH WLYHVVHP D PHVPD
HVWUXWXUDIRUPDQGRXPVLVWHPDKRPRJrQHRTXHYDLDGTXLULUPRELOLGDGHGHXPDVy
YH]DXPDWHPSHUDWXUDLQWHUPHGLiULDjV7JVGRVKRPRSROtPHURVSXURV


)LJXUD(IHLWRGDPLVFLELOLGDGHQDVWHPSHUDWXUDVGHWUDQVLomRYtWUHDGHPLVWXUDVSROLPpULFDV

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$7JGDPLVWXUDPLVFtYHOYDLGHSHQGHUGDFRPSRVLomRGHVVDPLVWXUDFRPRLOXVWUD
D)LJXUD8PPDLRUWHRUGRSROtPHUR$QDPLVWXUDPLVFtYHOID]FRPTXHD7J
HVWHMDPDLVGHVORFDGDSDUDRYDORUGD7JGRSROtPHUR$SXURHGRPHVPRPRGRXP
PDLRUWHRUGRSROtPHUR%ID]FRPTXHD7JGDPLVWXUDHVWHMDPDLVGHVORFDGDSDUDR
YDORUGD7JGRSROtPHUR%SXUR

)LJXUD(IHLWRGDFRPSRVLomRGHPLVWXUDSROLPpULFDPLVFtYHOQDWHPSHUDWXUDGHWUDQVLomRYtWUHD

possvel prever o valor da Tg?


2 YDORU GD 7J GD PLVWXUD PLVFtYHO RX FRSROtPHUR SRGH VHU SUHYLVWR SRU PHLR GH
GLYHUVDVHTXDo}HVLQLFLDOPHQWHHPStULFDVTXHIRUDPSURSRVWDVSDUDFDOFXODUD7JD
SDUWLU GRV YDORUHV GH 7J GRV FRPSRQHQWHV SXURV H GH VXDV SURSRUo}HV QD PLVWXUD
0DLV WDUGH IRUDP DSUHVHQWDGDV YiULDV WHRULDV TXH GHUDP HPEDVDPHQWR
WHUPRGLQkPLFR jV UHODo}HV SURSRVWDV $ SULPHLUD HTXDomR p D UHJUD GDV PLVWXUDV
TXHHVWDEHOHFHTXH
Tg AB = W A .Tg A + WB .Tg B (10.3)

RQGH 7J$ 7J% H 7J$% VmR DV 7JV GRV KRPRSROtPHURV $ H % SXURV H GD PLVWXUD $%
UHVSHFWLYDPHQWH H :$ H :% VmR DV IUDo}HV PiVVLFDV GRV FRPSRQHQWHV $ H % QD
PLVWXUD (VWD HTXDomR p DGHTXDGD D VLVWHPDV LGHDLV PLVFtYHLV H DPRUIRV FRP
LQWHUDo}HVIUDFDV4XDQGRHVWDHTXDomRQmRGHVFUHYHGHIRUPDDGHTXDGDRVYDORUHV
GH 7J GH VLVWHPDV GH PLVWXUDV ItVLFDV PLVFtYHLV H FRSROtPHURV DOHDWyULRV SRGH VHU
HPSUHJDGDDHTXDomRGH)R[QDTXDORYDORUGH7J$%pGDGRSRU

&DUDFWHUL]DomRGH3ROtPHURV  
1 W A WB
= + (10.4)
Tg AB Tg A Tg B
RXHQWmRSRUPHLRGDHTXDomRGH*RUGRQ7D\ORU
W ATgA + WBTgB
Tg = (10.5)
W A + kWB
RQGHNpXPSDUkPHWURGHILQLGRSHODUD]mRGDYDULDomRGRFRHILFLHQWHGHH[SDQVmR
WpUPLFD L HQWUHRHVWDGRERUUDFKRVRHRHVWDGRYtWUHRGRVKRPRSROtPHURV$H%
(VWH SDUkPHWUR WHP VLGR FRQVLGHUDGR SRU DOJXQV DXWRUHV FRPR XP LQGLFDGRU GD
LQWHQVLGDGHGDVLQWHUDo}HVSUHVHQWHVQRVLVWHPD
$7DEHODUHVXPHDVUHODo}HVXWLOL]DGDVSDUDSUHYHUDGHSHQGrQFLDGD7JFRP
D  FRPSRVLomR HP VLVWHPDV PLVWRV PLVFtYHLV EDVHDGDV QRV YDORUHV GH 7J GRV
FRPSRQHQWHVSXURV
eLPSRUWDQWHGHVWDFDUTXHQRFDVRGHVLVWHPDVTXHDSUHVHQWHPGXDV7JVHVWDV
GHYHPHVWDUVHSDUDGDVSHORPHQRVR&XPDGDRXWUDDILPGHTXHDDQiOLVHSRVVD
VHU EHP UHVROYLGD (QWmR SRGH VXUJLU D VHJXLQWH TXHVWmR VH R VLVWHPD IRU
SDUFLDOPHQWHPLVFtYHORXDWpPHVPRLPLVFtYHOHVXDV7JVVHMDPWmRSUy[LPDVTXHD
GLIHUHQoD HQWUH HODV QmR H[FHGD R& FRPR p SRVVtYHO DFRPSDQKDU SRU '6& D
PLVFLELOLGDGH GHVVH VLVWHPD VH D FXUYD Vy DSUHVHQWD XPD GHVFRQWLQXLGDGH
FDUDFWHUtVWLFDGHDSHQDVXPD7J"
(DUHVSRVWDDHVWDTXHVWmRpEDVWDQWHVLPSOHVQmRpSRVVtYHOGHYLGRjOLPLWDomR
GD WpFQLFD XWLOL]DGD XVDQGR D PHWRGRORJLD DWp DJRUD GLVFXWLGD (QWUHWDQWR WHRULDV
UHFHQWHV VXJHUHP XP WUDWDPHQWR WHyULFR EDVHDGR QD UD]mR HQWUH DV FDSDFLGDGHV
FDORUtILFDVGRVGRLVFRPSRQHQWHVHRVYDORUHVGH7JGRVFRPSRQHQWHVSXURV













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7DEHOD5HODo}HVSDUDSUHYHUDGHSHQGrQFLDGD7JFRPDFRPSRVLomRHPVLVWHPDVPLVWRVPLVFtYHLV

$XWRU (TXDomR 2EVHUYDomR


5HJUDGDV 6H7J$7J%DVIXQo}HVORJ
GD(TSRGHPVHU
PLVWXUDV Tg AB = W A .Tg A + WB .Tg B (10.3)
H[SDQGLGDV

1 W A WB (10.4) 6H &SL7JL IRUFRQVWDQWH


)R[ = +
Tg AB Tg A Tg B HVWD(TLJXDODVHj(T

*RUGRQ WATgA + WBTgB


Tg = (10.5) K = B / A
7D\ORU WA + kWB

W T + kW TgB
&RXFKPDQ Tg =
A gA B
(10.6)
$GHTXDGDSLQWHUDo}HV
VHPHOKDQWHD WA + kWB
HVSHFtILFDVPXLWRIUDFDVRX
GH*RUGRQ
sendo k = Cp B DXVHQWHVTgA/TgB 1
7D\ORU 
Cp A

W A Cp A ln Tg A + W B Cp B ln Tg B (10.7) (TXDomRWHyULFDTXHGiRULJHP
&RXFKPDQ ln Tg AB =
jVGHPDLV
W A Cp A + W B Cp B

W A Cp ATg A + W B Cp B Tg B (10.8) 6H7J$7J%D(TSRGH


&RXFKPDQ Tg AB =
W A Cp A + W B Cp B VHUVLPSOLILFDGD

%HDWW\H ln Tg AB = W A . ln Tg A + WB . ln Tg B (10.9) 6H&S$ &S%HVWD(T


3RFKDQ LJXDODVHj(T
$UD]mR Cp B pXVDGD
K=
Cp A
8WUDFNL WA . ln TgA + kWB . ln TgB (10.10)
ln Tg AB =
WA + kWB QD(T

&RXFKPDQH A A .Tg A + B B Tg B (10.11)


Tg AB = 9PJ9PO
.DUDV] A A + B B

8WUDFNLH Wn Cp n . ln Tg n (10.12)
ln Tg AB = 3DUDVLVWHPDVPXOWLFRPSRQHQWHV
&RXFKPDQ Wn Cp n

$H%VmRDVGLIHUHQoDVQRFRHILFLHQWHGHH[SDQVmRWpUPLFDQRHVWDGRYtWUHRHQRHVWDGRERUUDFKRVRSDUD
XPFRPSRQHQWHQpRQ~PHURGHFRPSRQHQWHV

&DUDFWHUL]DomRGH3ROtPHURV  
10.3.8.5 Estudo de morfologia em funo do tratamento trmico
2 HIHLWR GR WUDWDPHQWR WpUPLFR VREUH D PRUIRORJLD GR SROtPHUR WDPEpP SRGH VHU
DFRPSDQKDGRSRU'6&9DPRVVXSRUDDQiOLVHGHXPKRPRSROtPHURVHPLFULVWDOLQR
3RUVHUVHPLFULVWDOLQRDFXUYDGH'6&LUiPRVWUDUXPD7JHXPD7PFRPRPRVWUDD
)LJXUD D $ DPRVWUD IRL FRORFDGD QD FiSVXOD H DTXHFLGD D R&PLQ DWp XPD
WHPSHUDWXUDDFLPDGDVXD7P$RILQDOGDDQiOLVH 7I DDPRVWUDHQFRQWUDVHIXQGLGD
GHQWURGDFiSVXOD$RSURFHGHUXPDDQiOLVHGHUHVIULDPHQWRDSDUWLUGH7IWDPEpPD
R&PLQDWp7LjPHGLGDTXHDDPRVWUDYDLVHQGRUHVIULDGDHODYDLVROLGLILFDQGRH
FRPRDDPRVWUDWHPWHQGrQFLDDIRUPDUXPDUUDQMRFULVWDOLQRHODVROLGLILFDGHPRGR
RUJDQL]DGR UHFRQVWUXLQGR VXDV UHJL}HV FULVWDOLQDV $ IRUPDomR GRV FULVWDLV p
REVHUYDGD SHOR DSDUHFLPHQWR GH XP SLFR H[RWpUPLFR FRUUHVSRQGHQWH j 7F
WHPSHUDWXUD GH FULVWDOL]DomR )LJXUD E  $R ILQDO GD DQiOLVH DJRUD j
WHPSHUDWXUDPDLVEDL[D 7L DDPRVWUDHQFRQWUDVHQRHVWDGRVyOLGRWHQGRDGTXLULGR
QRYDPHQWH PRUIRORJLD VHPLFULVWDOLQD $VVLP DR SURFHGHU QRYR DTXHFLPHQWR D
R&PLQDWp7IVHUiREVHUYDGDXPDFXUYDFRPRDGD)LJXUDD1HVWHSRQWRD
DPRVWUD HQFRQWUDVH QRYDPHQWH IXQGLGD QD FiSVXOD 6H DJRUD VXEPHWHUPRV HVWD
DPRVWUDDXPUHVIULDPHQWRUiSLGR TXHQFKLQJ DWp7L WHPSHUDWXUDDEDL[RGD7J 
HODYDLVROLGLILFDUSRUpPDVFDGHLDVQmRWHUmRWHPSRGHVHRUJDQL]DUHIRUPDUDV
UHJL}HV FULVWDOLQDV TXH OKHV VmR FDUDFWHUtVWLFDV $ DPRVWUD HQFRQWUDVH HQWmR QR
HVWDGRVyOLGRDPRUIRDSHVDUGDVXDWHQGrQFLDDFULVWDOL]DUIRUPDQGRXPSROtPHUR
VHPLFULVWDOLQR 6XEPHWHQGR HVWD DPRVWUD QRYDPHQWH D XP SURJUDPD GH
DTXHFLPHQWR R&PLQ  DWp 7I DV FDGHLD LUmR DGTXLULU PRELOLGDGH QD 7J H D XPD
WHPSHUDWXUD DFLPD GD 7J DV FDGHLDV WHUmR PRELOLGDGH VXILFLHQWH SDUD VH RUJDQL]DU
VHJXLQGRVXDWHQGrQFLDLVWRpKDYHUiDIRUPDomRGHUHJL}HVFULVWDOLQDVHXPSLFR
H[RWpUPLFR UHODWLYR j 7F SRGH VHU REVHUYDGR )LJXUD F  3URVVHJXLQGR FRP R
DXPHQWRGDWHPSHUDWXUDRVFULVWDLVIRUPDGRVVRIUHUmRIXVmRHRSLFRHQGRWpUPLFR
UHODWLYRj7PSRGHVHUREVHUYDGR )LJXUDF 0DLVXPDYH]DDPRVWUDHQFRQWUD
VHQDFiSVXODQRHVWDGRIXQGLGRSURQWDSDUDTXDOTXHUWLSRGHWUDWDPHQWRWpUPLFR
GHVHMDGR

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)LJXUD(IHLWRGRWUDWDPHQWRWpUPLFRVREUHDVWUDQVLo}HVGHXPSROtPHURVHPLFULVWDOLQR

10.3.8.6 Estudo de cintica de cristalizao


8PD DPRVWUD GH SROtPHUR VHPLFULVWDOLQR HP XPD DQiOLVH GH DTXHFLPHQWR D
R&PLQ GHQWUR GR LQWHUYDOR GH WHPSHUDWXUD DGHTXDGR Gi RULJHP D XPD FXUYD
FRP7JH7P$RILPGDDQiOLVHRSROtPHURHQFRQWUDVHQRHVWDGRIXQGLGRHVHXP
UHVIULDPHQWR UiSLGR DWp 77J p UHDOL]DGR D DPRVWUD VROLGLILFD VHP TXH KDMD
IRUPDomRVLJQLILFDWLYDGHUHJL}HVFULVWDOLQDVSRUTXHDEDL[RGD7JDVFDGHLDVQmRWrP
PRELOLGDGH VXILFLHQWH SDUD GLIXQGLU H VH RUJDQL]DU HP DUUDQMRV FULVWDOLQRV 6H D
DPRVWUDIRUUHVIULDGDUDSLGDPHQWHDWpXPDWHPSHUDWXUDHQWUHD7JHD7PHPDQWLGD

&DUDFWHUL]DomRGH3ROtPHURV  
QHVWD WHPSHUDWXUD GXUDQWH XP GHWHUPLQDGR WHPSR DQQHDOLQJ  DV FDGHLDV
WHQGHUmR D FULVWDOL]DU SRLV H[LVWH PRELOLGDGH VXILFLHQWH SDUD TXH RFRUUD HVVD
RUJDQL]DomR $VVLP XP SLFR H[RWpUPLFR UHODWLYR j 7F SRGH VHU REVHUYDGR e IiFLO
SHUFHEHUTXHTXDQWRPDLVSUy[LPRGD7JRXGD7PIRUDWHPSHUDWXUDVHOHFLRQDGDD
GLILFXOGDGHGHFULVWDOL]DomRDXPHQWDSRUPRWLYRVGLVWLQWRV3Uy[LPRj7JDVFDGHLDV
HVWmR SHUGHQGR PRELOLGDGH H QmR FRQVHJXHP VH GLIXQGLU SDUD VH RUJDQL]DUHP
3Uy[LPR j 7P D PRELOLGDGH GDV FDGHLDV p PXLWR JUDQGH SDUD PDQWHU XP DUUDQMR
RUJDQL]DGR SHUPDQHQWH $ SULQFtSLR D TXDOTXHU WHPSHUDWXUD DFLPD GD 7J H DEDL[R
GD 7P p SRVVtYHO SURFHGHU D XPD FULVWDOL]DomR QXP SURFHVVR LVRWpUPLFR FRP R
WHPSR3RUpPGHSHQGHQGRGDWHPSHUDWXUDDYHORFLGDGHGHFULVWDOL]DomRLUiYDULDU
2HVWXGRGHFLQpWLFDGHFULVWDOL]DomRpIHLWRFRPEDVHQRFRPSRUWDPHQWRGHVFULWR
DFLPD$DPRVWUDpPDQWLGDDXPDGHWHUPLQDGDWHPSHUDWXUDHQWUHD7JHD7PHXP
SLFRH[RWpUPLFRpREVHUYDGR )LJXUD $DPRVWUDOHYDXPGHWHUPLQDGRWHPSR
DWpDWLQJLURPi[LPRGHFULVWDOL]DomR

)LJXUD3LFRGHFULVWDOL]DomRREVHUYDGRGXUDQWHXPH[SHULPHQWRLVRWpUPLFR

$HTXDomRGH$YUDPLUHODFLRQDDIUDomRGRPDWHULDOFULVWDOL]DGRQRWHPSRW[ W 
FRPDFRQVWDQWHGHYHORFLGDGHGHFULVWDOL]DomRJOREDONGRVHJXLQWHPRGR
kt n
x(t ) = 1 e (10.13)

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RQGH Q p R H[SRHQWH GH $YUDPL R TXDO GHVFUHYH R PHFDQLVPR GH FULVWDOL]DomR H
IRUQHFH LQIRUPDomR TXDOLWDWLYD VREUH D QDWXUH]D GRV SURFHVVRV GH QXFOHDomR H
FUHVFLPHQWRGRVFULVWDLV2VHXYDORUSRGHYDULDUGHD

$ IUDomR GR PDWHULDO FULVWDOL]DGR p REWLGD SRU LQWHJUDomR GD iUHD VRE R SLFR
H[RWpUPLFRDLQWHUYDORVGHWHPSRSUpGHWHUPLQDGRVGHDFRUGRFRPDHTXDomR
dHt
0 dt dt
x (t ) =
dH
0 dt dt (10.14)
WRPDQGRW FRPRRLQVWDQWHHPTXHVHDWLQJHRHTXLOtEULRWpUPLFRHW FRPR
RILQDOGRSURFHVVRGHFULVWDOL]DomRHRQGHG+GWpDWD[DGHIOX[RGHFDORUH[ W pD
IUDomRHPPDVVDGHPDWHULDOFULVWDOL]DGRQRWHPSRW
&RQVLGHUDQGR TXH DV LQWHJUDLV UHSUHVHQWDP iUHDV D HTXDomR DFLPD SRGH VHU
HVFULWDQDIRUPD
At
x(t ) = (10.15)
A
RQGH$WpDiUHDVREDFXUYDGHFULVWDOL]DomRGHVGHRLQVWDQWH]HURDWpRLQVWDQWHWH
$pDiUHDWRWDOVREDFXUYDGHFULVWDOL]DomR
$JUDQGH]D[ W UHODFLRQDRJUDXGHFULVWDOLQLGDGHGHVHQYROYLGRHPFDGDLQVWDQWH
FRP D FULVWDOLQLGDGH WRWDO DVVRFLDGD D GHWHUPLQDGDV FRQGLo}HV H[SHULPHQWDLV
3RUWDQWRRYDORUQRUPDOL]DGRGH[ W YDULDGH]HURD
$SDUWLUGRSLFRH[RWpUPLFRREWpPVHRVYDORUHVGH[ W HPIXQomRGHW

Como utilizar esses valores para chegar em k e n ?


$(TXDomRGH$YUDPLSRGHVHUPDWHPDWLFDPHQWHUHDUUDQMDGDGRVHJXLQWHPRGR
n)
x(t ) = 1 e ( kt
n)
1 x(t ) = e ( kt

ln1 ln x(t ) = kt n (10.16)

&DUDFWHUL]DomRGH3ROtPHURV  
ln[(ln1 ln x(t )] = n ln kt
ln{ ln[1 x(t )]}= n ln kt
(VWD H[SUHVVmR p D HTXDomR GH XPD UHWD 8VDQGR RV YDORUHV GH [ W  REWLGRV GR
SLFRH[RWpUPLFRSDUDFRQVWUXLUXPJUiILFRGHOQ^OQ>[ W @`YHUVXVOQWGRFRHILFLHQWH
DQJXODU REWHUHPRV RV YDORUHV GH Q H N D SDUWLU GRV FRHILFLHQWHV DQJXODU H OLQHDU
UHVSHFWLYDPHQWH
2YDORUGRH[SRHQWHGH$YUDPLHVWiUHODFLRQDGRFRPDJHRPHWULDGHFUHVFLPHQWR
FRPRPRVWUDD7DEHOD
7DEHOD9DORUHVGRH[SRHQWHGH$YUDPLGHDFRUGRFRPDJHRPHWULDGHFUHVFLPHQWRGRFULVWDO

*HRPHWULD
GH 1XFOHDomR
FUHVFLPHQWR
 ,QVWDQWkQHD (VSRUiGLFD +HWHURJrQHD
(VIHUXOLWR   !Q!
'LVFR   !Q!
%DVWmR   !Q!

$YHORFLGDGHHPHFDQLVPRGHFULVWDOL]DomRSRGHPYDULDUFRPDWHPSHUDWXUDQD
TXDO D DPRVWUD IRL LQGX]LGD D FULVWDOL]DU )D]HQGRVH YiULDV LVRWHUPDV GH
FULVWDOL]DomR D WHPSHUDWXUDV YDULDGDV HQWUH D 7J H D 7P VHUmR REWLGDV FXUYDV
GLVWLQWDVFRPRPRVWUDD)LJXUD
3DUD FDGD XPD GHVWDV LVRWHUPDV SRGH VHU IHLWR R PHVPR WUDWDPHQWR GHVFULWR
DFLPDHREWHUHPRVXPYDORUGHNHQSDUDFDGDWHPSHUDWXUD

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10.3.8.7 Determinao de porcentagem de cristalinidade


$VDPRVWUDVGHSROtPHURVSRGHPVHUHQFRQWUDGDVHPGLYHUVRVJUDXVGHRUJDQL]DomR
GH VXDV FDGHLDV 8PD DPRVWUD QD TXDO DV FDGHLDV HQFRQWUDPVH WRWDOPHQWH

&DUDFWHUL]DomRGH3ROtPHURV  
GHVRUJDQL]DGDV p GHQRPLQDGD DPRUID 6H DV FDGHLDV SXGHVVHP HVWDU WRWDOPHQWH
RUJDQL]DGDV D DPRVWUD VHULD GHQRPLQDGD WRWDOPHQWH FULVWDOLQD &RPR YLVWR
DQWHULRUPHQWH HVWD FRQGLomR GH FRPSOHWD RUJDQL]DomR DLQGD QmR IRL REVHUYDGD QD
SUiWLFD SDUD QHQKXP WLSR GH SROtPHUR ( RV SROtPHURV TXH WHQGHP D DSUHVHQWDU
FDGHLDV GLVWULEXtGDV HP UHJL}HV DPRUIDV H FULVWDOLQDV RUJDQL]DGDV HQWUH VL VmR
GHQRPLQDGRV VHPLFULVWDOLQRV 'HSHQGHQGR GH IDWRUHV WDLV FRPR
HVWHUHRUUHJXODULGDGHVLPHWULDHQWUHRXWURVRVSROtPHURVLUmRDSUHVHQWDUPDLRURX
PHQRU WHQGrQFLD D FULVWDOL]DU $ UHODomR HQWUH D UHJLmR DPRUID H FULVWDOLQD GH XPD
DPRVWUD GH SROtPHUR p H[SUHVVD HP WHUPRV GH SRUFHQWDJHP GH FULVWDOLQLGDGH RX
JUDX GH FULVWDOLQLGDGH $ YDULDomR QD SRUFHQWDJHP GH FULVWDOLQLGDGH LUi DIHWDU
GLUHWDPHQWHGLYHUVDVSURSULHGDGHVGRPDWHULDO$SRUFHQWDJHPGHFULVWDOLQLGDGHGH
XPSROtPHURSRGHVHUGHWHUPLQDGDSRU'6&DSDUWLUGRSLFRHQGRWpUPLFRUHODWLYRj
IXVmR FULVWDOLQD $ iUHD VRE R SLFR HVWi GLUHWDPHQWH UHODFLRQDGD j TXDQWLGDGH GH
FDORU DEVRUYLGD QD IXVmR 6H XP PDLRU WHRU GD DPRVWUD DSUHVHQWDVH QD IRUPD GH
DUUDQMRRUJDQL]DGR PDLVUHJL}HVFULVWDOLQDVRXPDLRUJUDXGHFULVWDOLQLGDGH HQWmR
XPDPDLRUTXDQWLGDGHGHFDORUVHUiDEVRUYLGDQDIXVmR2RSRVWRpREVHUYDGRSDUD
DPRVWUDVFRPSHTXHQDSRUFHQWDJHPGHUHJL}HVFULVWDOLQDV/RJRDSRUFHQWDJHPGH
FULVWDOLQLGDGHpFDOFXODGDGLUHWDPHQWHSRU
H f A
% de cristalinidade = x 100 (10.17)
H f A 100% cristalino
RQGH +I $ p D YDULDomR GH HQWDOSLD GH IXVmR GD DPRVWUD GH SRUFHQWDJHP GH
FULVWDOLQLGDGHGHVFRQKHFLGDH+I$FULVWDOLQRpDYDULDomRGHHQWDOSLDGHIXVmRSDUDD
DPRVWUDFULVWDOLQD
2YDORUGH+IGDDPRVWUDFULVWDOLQDpHQFRQWUDGRWDEHODGRSDUDXPDVpULH
GH SROtPHURV 3RUpP SDUHFH XP WDQWR HVWUDQKR WUDWDU GH +I  GD DPRVWUD 
FULVWDOLQD VH QR SDUiJUDIR DQWHULRU IRL FLWDGD D LPSRVVLELOLGDGH SUiWLFD GH VH REWHU
XPD DPRVWUD  FULVWDOLQD 1D YHUGDGH H[LVWHP DOJXQV PRGRV GLVWLQWRV GH VH
FKHJDU DR YDORU GH +I  GH XPD DPRVWUD  FULVWDOLQD H XP GHOHV EDVHLDVH QD
FDUDFWHUL]DomRGHYiULDVDPRVWUDVGHXPPHVPRSROtPHURFRPGLIHUHQWHVJUDXVGH
FULVWDOLQLGDGH(VWDVDPRVWUDVWrPDSRUFHQWDJHPGHFULVWDOLQLGDGHGHWHUPLQDGDSRU
XPD WpFQLFD GLUHWD FRPR SRU H[HPSOR GLIUDomR GH UDLRV; H RV YDORUHV GH +I
GHWHUPLQDGRV SHOD SUySULD WpFQLFD GH '6& &RQVWUXLQGRVH XP JUiILFR GH
SRUFHQWDJHPGHFULVWDOLQLGDGHYHUVXV+IpSRVVtYHOVHREWHUR+IGDDPRVWUD
FULVWDOLQDSRUH[WUDSRODomR

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10.3.8.8 Identificao de componentes de misturas de polmeros semi-
cristalinos
2 '6& WDPEpP SRGH VHU XWLOL]DGR SDUD LGHQWLILFDomR GH FRPSRQHQWHV HP PLVWXUDV
GH KRPRSROtPHURV VHPLFULVWDOLQRV &RPR Mi PHQFLRQDGR D LQWHUSHQHWUDomR GH
FDGHLDV GH SROtPHURV GLVWLQWRV QDV UHJL}HV DPRUIDV HVWi UHODFLRQDGD j DILQLGDGH
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10.3.8.9 Determinao de composio de misturas de polmeros


semicristalinos
$ FRPSRVLomR GH PLVWXUDV ItVLFDV GH SROtPHURV RV TXDLV SRVVXHP 7PV VXILFLHQ
WHPHQWHGLIHUHQWHVSRGHVHUGHWHUPLQDGDSRU'6&DWUDYpVGHXPDUHODomRHQWUHRV
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PLVWXUDV GH GRLV KRPRSROtPHURV VHPLFULVWDOLQRV D R&PLQ QR LQWHUYDOR GH WHP
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e LPSRUWDQWH REVHUYDU TXH FRPR D iUHD GR SLFR YDULD FRP R JUDX GH
FULVWDOLQLGDGHDFXUYDGHFDOLEUDomRGHYHVHUREWLGDDSDUWLUGHDPRVWUDVFRPJUDXV
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R'6&PRGXODGRHDIRWRFDORULPHWULDGLIHUHQFLDO

10.4 Calorimetria diferencial de varredura modulada (MDSC)


8P GRV GHVHQYROYLPHQWRV PDLV VLJQLILFDWLYRV HP DQiOLVH WpUPLFD QRV ~OWLPRV RLWR
DQRV IRL R ODQoDPHQWR GH XP LQVWUXPHQWR FRPHUFLDO TXH HPSUHJD D WpFQLFD
FRQKHFLGDFRPR'6&PRGXODGR 0'6& 2VWHUPRV'6&RVFLODWyULRRX'6&DOWHUQDGR
WDPEpP VmR XVDGRV SDUD GHVFUHYHU HVWH PpWRGR 2 '6& PRGXODGR HPSUHJD R
PHVPR SULQFtSLR HVVHQFLDO GH IOX[R GH FDORU GHVFULWR SDUD R '6& FRQYHQFLRQDO $V
GLIHUHQoDVFKDYHHVWmRQRPpWRGRH[SHULPHQWDOHQDDQiOLVHGHGDGRVGLVSRQtYHLVD
SDUWLU GHVWHV H[SHULPHQWRV 8PD PRGXODomR VHQRLGDO p DSOLFDGD VREUH D WD[D GH
DTXHFLPHQWRRXUHVIULDPHQWROLQHDUFRQYHQFLRQDOSDUDSURGX]LUXPSHUILOQRTXDOD
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FDSDFLGDGHGHFRPELQDUWD[DVGHDTXHFLPHQWRDOWDVLQVWDQWkQHDVFRPXPDWD[DGH
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Qual a importncia da medida ser resolvida em duas componentes?


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YiULRV LQLFLDGRUHV TXtPLFRV VREUH D YHORFLGDGH GH FXUD GH VLVWHPDV SROLPpULFRV 2
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Anlises Termomecnicas:
Anlise Termomecnica
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Termodinmico-mecnica
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11.1 Deformaes mecnicas em materiais


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11.2.1 Introduo
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2V YiULRV PpWRGRV GH DQiOLVH WHUPRPHFkQLFD GHYHP VHU XWLOL]DGRV FRP RV
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WHPSHUDWXUD GHWHFWDGD WDPEpP GHYH YLU DFRPSDQKDGR GR PRGR GH RSHUDomR
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FRPSXWDGRUTXHSURFHVVDRGDGRHPFRQMXQWRFRPDPHGLGDHIHWXDGDSHODVRQGD
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SDGU}HV TXH SRGHP VHU SRU H[HPSOR RV HOHPHQWRV tQGLR ,Q  H HVWDQKR 6Q  p
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11.2.3 Modo de expanso


2V HQVDLRV GH H[SDQVmR VmR HIHWXDGRV GH PRGR D IRUQHFHU RV FRHILFLHQWHV GH
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IXVmR

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R LQtFLR GD WUDQVLomR (VWH SRQWR p REWLGR SHOD LQWHUVHomR GRV SURORQJDPHQWRV GH
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2V HQVDLRV GH FRPSUHVVmR VmR UHDOL]DGRV GH PRGR D REWHU LQIRUPDo}HV VREUH D
GHIRUPDomR VRIULGD SHOD DPRVWUD VRE XP HVIRUoR FRQVWDQWH GH FRPSUHVVmR FRP D
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11.2.5 Modo de penetrao


2 PRGR RSHUDFLRQDO GH SHQHWUDomR SHUPLWH D LGHQWLILFDomR GR SRQWR GH
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H[HPSOR GH XPD PDWHULDO SROLPpULFR TXH FRP R DXPHQWR GD WHPSHUDWXUD
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GD OHLWXUD LQLFLDO 2 PpWRGR PDLV LQGLFDGR VHULD D GHWHUPLQDomR GR SRQWR GH
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11.2.6 Modo de flexo


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1HVWHPRGRGHHQVDLRXPSHTXHQRSHGDoRGHILOPHUHWDQJXODUSRGHVHUXVDGR
FRPRFRUSRGHSURYDRTXDOpVXEPHWLGRDXPDFDUJD$VGLPHQV}HVGDVXSHUItFLH
GR ILOPH VmR GH PP [ PP $ FDUJD D VHU XWLOL]DGD QR H[SHULPHQWR p REWLGD HP
IXQomRGRYDORUGDHVSHVVXUDGRFRUSRGHSURYDVHJXQGRD(TXDomR

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LGHQWLILFDVHDWHPSHUDWXUDGHRFRUUrQFLDGDGHIOH[mRGRPDWHULDO )LJXUD 

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11.2.7 Exemplos de aplicao


$R ORQJR GR WH[WR DOJXPDV DSOLFDo}HV GR 70$ Mi IRUDP FLWDGDV WDLV FRPR D
GHWHUPLQDomRGH
SWHPSHUDWXUDGHWUDQVLomRYtWUHD
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SDeterminao do valor de mdulo
$ FDUDFWHUL]DomR GR PyGXOR GH XP PDWHULDO FRP R DX[tOLR GR 70$ QmR p
QHFHVVDULDPHQWH GLVWLQWD GDV WpFQLFDV FRQYHQFLRQDLV 7DLV WpFQLFDV FRPR $670 '
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QRVGHFRPSUHVVmR2SURFHGLPHQWRGRVWHVWHVGHFRPSUHVVmRWHPDOJXPDVIDOKDV
2XVRGHGLIHUHQWHVFRQILJXUDo}HVGDVDPRVWUDVDIHWDDVUHVSRVWDV3RUH[HPSORRV
GDGRVREWLGRVDSDUWLUGHFRUSRVGHSURYDFLOtQGULFRVHUHWDQJXODUHVQmRSRGHPVHU
FRPSDUDGRV
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PXLWDV YH]HV p GLIHUHQFLDGD SDUD GLYHUVRV SROtPHURV H HP GLIHUHQWHV UHJL}HV
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$SULQFLSDOGLVWLQomRHQWUHHQVDLRVGHFRPSUHVVmRSRU70$HRVFRQYHQFLRQDLVp
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GHWHUPLQDGD YDULDomR GH WHPSHUDWXUD (VWH PpWRGR p FDSD] GH GHVFUHYHU R
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PyGXORGH<RXQJQHVWHFDVRpREWLGRSRULQWHUPpGLRGD(TXDomR
E =
(
3PR 1 2 ) [x 1/ 2
+ 0,252 x + 0,1588 x 3 / 2 + 0,2245 x 2 + 0,3069 x 5 / 2 + 0,2980 x 3 ]
3
3
4H (11.5)
VHQGR[REWLGRSHODUHODomR
Rd
x =
2
H

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DUD]mRGH3RLVVRQ
$(TXDomRDSUHVHQWDDSRVVLELOLGDGHGHFRUUHomRGHDOJXPDVGLVWRUo}HVGRV
WHVWHV GH FRPSUHVVmR $ GHWHUPLQDomR GR PyGXOR HP IXQomR GD UD]mR GH 3RLVVRQ
IDFLOLWD SRU H[HPSOR D FRUUHomR UHODWLYD DRV HVWDGRV YLVFRHOiVWLFRV 3ROtPHURV
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HVWDGR ItVLFR RX VHMD HP GLIHUHQWHV WHPSHUDWXUDV &RQWXGR D SULQFLSDO FRUUHomR
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XP HVIRUoR DSUHVHQWD XPD UHDomR TXH p IXQomR GH GRLV IDWRUHV EiVLFRV L  VXD
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$ DYDOLDomR GD UHVSRVWD HOiVWLFD FRP UHODomR j XWLOL]DomR GH XPD SRQWD GH IRUPD
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([SHULPHQWDOPHQWHSDUDRFiOFXORGRPyGXORGH<RXQJDSDUWLUGHUHVXOWDGRVGH
70$ p QHFHVViULR REWHU GR FRPSXWDGRU RV YDORUHV UHODWLYRV jV GHIRUPDo}HV GR
FRUSRGHSURYD3DUDFDGDDPRVWUDHSDUDFDGDDTXHFLPHQWRVRIULGRpGHWHUPLQDGR
XP YDORU GH DOWXUD LQLFLDO D XPD GHWHUPLQDGD WHPSHUDWXUDEDVH TXH GHSHQGH GR
VLVWHPD SROLPpULFR HP DQiOLVH $SyV HVWD HWDSD VmR HVFROKLGDV WHPSHUDWXUDV TXH
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FRUUHVSRQGHQWHV 3RU H[HPSOR SDUD XPD WHPSHUDWXUDEDVH GH & SRGHP VHU
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WHPSHUDWXUD SDUD XPD DPRVWUD SROtPHUR QR HVWDGR DPRUIR H QR HVWDGR
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&DUDFWHUL]DomRGH3ROtPHURV 
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REWLGDVSRUPHLRGHDQiOLVHWHUPRPHFkQLFD

SVariao da Tg com o grau de cura


$ YDULDomR GD 7J FRP R JUDX GH FXUD SRGH VHU PRQLWRUDGD SRU DQiOLVH
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HPWHPSRVGLIHUHQWHV WW 2EVHUYDVHTXHD7JDXPHQWDFRPRDXPHQWRGRJUDX
GHFXUD

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QDPHVPDWHPSHUDWXUDGXUDQWHRVWHPSRV D WH E WVHQGRWW

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11.3 Viscoelasticidade
$WpDTXLIRLDERUGDGRRFRQFHLWRGHPyGXORUHODFLRQDGRDRFRPSRUWDPHQWRHOiVWLFR
GRVPDWHULDLV9DPRVGLVFXWLUXPSRXFRPDLVVREUHRFRPSRUWDPHQWRPHFkQLFRGRV
PDWHULDLV
6yOLGRV SHUIHLWDPHQWH HOiVWLFRV TXDQGR VXEPHWLGRV D XPD GHIRUPDomR
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DSUHVHQWDP XP FRPSRUWDPHQWRYLVFRHOiVWLFRLQWHUPHGLiULRHQWUHVyOLGRHOtTXLGR
SDUWHGDHQHUJLDpDUPD]HQDGDHSDUWHpGLVVLSDGDVREDIRUPDGHFDORU
(P JHUDO RV SROtPHURV SRGHP H[LVWLU HP GLIHUHQWHV HVWDGRV PHFkQLFRV HP
IXQomRGDWHPSHUDWXUDHRXWHPSR pIiFLOLPDJLQDUTXHXPSOiVWLFRTXHDSUHVHQWD
XPD FHUWD ULJLGH] j WHPSHUDWXUD DPELHQWH SRGH WRUQDUVH XP PDWHULDO PDLV IOH
[tYHOVHVXEPHWLGRDXPDWHPSHUDWXUDPDLVHOHYDGD (VWHVHVWDGRVSRGHPVHUGLYL
GLGRVHPWLSRVSULQFLSDLV
S(VWDGRYtWUHR VyOLGRHOiVWLFROLQHDU 
S(VWDGRHOiVWLFRFRPHODVWLFLGDGHUHWDUGDGD VyOLGRYLVFRHOiVWLFR 
S(VWDGRHOiVWLFRFRPHODVWLFLGDGHLQVWDQWkQHD IOXLGRYLVFRHOiVWLFR 
S(VWDGRYLVFRVR IOXLGRYLVFRVROLQHDU 

$ )LJXUD  PRVWUD XP GLDJUDPD GH GHIRUPDomR UHVSRVWD GH FDGD WLSR GH
FRPSRUWDPHQWRPHQFLRQDGRDFLPDTXDQGRXPDWHQVmRpDSOLFDGD )LJXUDD 
PDQWLGDGXUDQWHXPGHWHUPLQDGRWHPSRHHQWmRUHWLUDGD2HVWDGRPHFkQLFRGH
FRPSRUWDPHQWRGHVyOLGRHOiVWLFROLQHDU )LJXUDE DSUHVHQWDXPDGHIRUPDomR
UHVSRVWDLQVWDQWkQHDTXHVHPDQWpPFRQVWDQWHGXUDQWHRWHPSRHPTXHDWHQVmRp
PDQWLGDHpWRWDOPHQWHUHFXSHUDGDSDUDDVGLPHQV}HVRULJLQDLVTXDQGRDWHQVmRp
UHWLUDGD1HVWHFDVRWHPRVTXHDXPDWHQVmRFRQVWDQWH DGHIRUPDomRUHVSRVWD
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SURSRUFLRQDOLGDGHRPyGXORGRVyOLGR ( 
o
E= (11.6)
o

&DUDFWHUL]DomRGH3ROtPHURV 
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DSOLFDGD+LVWyULDGHGHIRUPDomRFRUUHVSRQGHQWHSDUD E VyOLGRHOiVWLFROLQHDU F IOXLGRYLVFRVROLQHDU G 
VyOLGRYLVFRHOiVWLFR H IOXLGRYLVFRHOiVWLFR

2FRPSRUWDPHQWRUHSUHVHQWDGRQD)LJXUDFpRGHXPIOXLGRYLVFRVROLQHDU
1RWH TXH QHVWH FDVR D GHIRUPDomR QmR p LQVWDQWkQHD HOD DXPHQWD JUDGXDOPHQWH
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UHPRomR GD WHQVmR R IOXLGR PDQWpPVH GHIRUPDGR QmR UHFXSHUDQGR VXDV
GLPHQV}HVRULJLQDLV,VWRVLJQLILFDTXHGXUDQWHDDSOLFDomRGHXPDWHQVmRFRQVWDQWH

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 RFRUUH XPD YDULDomR OLQHDU GD GHIRUPDomR  o  WD[D GH GHIRUPDomR 
UHODFLRQDGDV HQWUH VL SRU XPD FRQVWDQWH GH SURSRUFLRQDOLGDGH D YLVFRVLGDGH GR
IOXLGR 
o
= (11.7)
 o
$V UHVSRVWDV GRV PDWHULDLV UHSUHVHQWDGDV QDV )LJXUDV G H H VmR GRLV
H[HPSORV GH FRPSRUWDPHQWRV LQWHUPHGLiULRV HQWUH XP VyOLGR HOiVWLFR OLQHDU H XP
IOXLGRYLVFRVROLQHDUTXHVmRFRPSRUWDPHQWRVYLVFRHOiVWLFRV

11.4 Anlise dinmico-mecnica (DMA) ou anlise termodinmico-


mecnica (DMTA)
$ DQiOLVH GH '07$ p FDSD] GH IRUQHFHU LQIRUPDo}HV D UHVSHLWR GR FRPSRUWDPHQWR
YLVFRHOiVWLFR GR VLVWHPD GHVPHPEUDQGR R PyGXOR HP GXDV FRPSRQHQWHV D
FRQWULEXLomRHOiVWLFDHDYLVFRVD

11.4.1 Introduo
1HVWH WLSR GH H[SHULPHQWR D WHQVmR RX D GHIRUPDomR p XPD IXQomR RVFLODWyULD
QRUPDOPHQWH VHQRLGDO FRP XPD IUHTrQFLD DQJXODU  I  6XSRQKDPRV TXH R
QRVVR HTXLSDPHQWR DSOLTXH XPD GHIRUPDomR VHQRLGDO GR WLSR = o sen( t )  H
PHoD D WHQVmR UHVSRVWD FRPR XPD IXQomR GD YDULDomR GD WHPSHUDWXUD RX GD
IUHTrQFLD(VVDWHQVmRUHVSRVWDLUiGHSHQGHUGRFRPSRUWDPHQWRGRPDWHULDO
0DWHPDWLFDPHQWH p SRVVtYHO DFRPSDQKDU FRPR DV LQIRUPDo}HV D UHVSHLWR GDV
FRQWULEXLo}HVHOiVWLFDHYLVFRVDGRPDWHULDOSRGHPVHUREWLGDV
6H XP FRUSR GH FRPSRUWDPHQWR HOiVWLFR LGHDO p VXEPHWLGR D XPD GHIRUPDomR
VHQRLGDOGRWLSR
= o sen ( t ) (11.8)

RQGH R p D DPSOLWXGH Pi[LPD GD GHIRUPDomR D WHQVmR UHVSRVWD WDPEpP VHUi


VHQRLGDOHHVWDUiHPIDVHFRPDGHIRUPDomRLVWRp
= o sen ( t ) (11.9)

FRPR
o
E= (11.10)
o

&DUDFWHUL]DomRGH3ROtPHURV 
HQWmRDGHIRUPDomRUHVSRVWDSRGHVHUHVFULWDFRPR
= E o sen ( t ) (11.11)

3DUDXPFRUSRGHFRPSRUWDPHQWRYLVFRVRLGHDODWHQVmRUHVSRVWDWDPEpPVHUi
GRWLSRVHQRLGDOSRUpPHVWDUiRIRUDGHIDVHFRPDGHIRUPDomR3DUDIOXLGRVD
WHQVmRHDWD[DGHGHIRUPDomRHVWmRUHODFLRQDGDVHQWUHVLSHODYLVFRVLGDGH

= (11.12)

HQWmR 
=  (11.13)

&RPRDGHIRUPDomRDSOLFDGDp = o sen ( t )HQWmR


d
 = = o cos( t ) (11.14)
dt
HDWHQVmRUHVSRVWDp
= o cos( t ) (11.15)

3DUDXPFRUSRGHFRPSRUWDPHQWRYLVFRHOiVWLFROLQHDUDWHQVmRUHVSRVWDVHUiGR
WLSRVHQRLGDOHHVWDUiGHIDVDGDGDGHIRUPDomRSRUXPFHUWRkQJXOR   
LVWRpFRPR
= o sen ( t ),
HQWmR
= o sen ( t + ) (11.16)


$ HTXDomR GD WHQVmR UHVSRVWD SRGH VHU GHVHQYROYLGD DSOLFDQGRVH D UHJUD GH
VHQ $%  VHQ$FRV%VHQ%FRV$HREWpPVHHQWmR
= o sen ( t )cos + o cos( t )sen (11.17)





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(VWD ~OWLPD HTXDomR PRVWUD TXH D WHQVmR UHVSRVWD SRGH VHU UHVROYLGD HP GXDV
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( )
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UHODFLRQDGDjHQHUJLDHOiVWLFDDUPD]HQDGD
( )
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HVWiUHODFLRQDGDjHQHUJLDYLVFRVDGLVVLSDGD

'LYLGLQGRVHFDGDXPDGHVVDVFRPSRQHQWHVGDWHQVmRUHVSRVWDSHODGHIRUPDomR
VHQRLGDODSOLFDGDREWrPVHGXDVFRPSRQHQWHVHPWHUPRVGHPyGXOR
o sen ( t )
E = cos (11.18)
o sen ( t )
H
o cos( t )
E = sen (11.19)
o sen ( t )
2PyGXORRULXQGRGDFRPSRQHQWHGDWHQVmRUHVSRVWDHPIDVHFRPDGHIRUPDomR
(pGHQRPLQDGRPyGXORGHDUPD]HQDPHQWR(RPyGXORRULXQGRGDFRPSRQHQWH
GHWHQVmRUHVSRVWDRIRUDGHIDVHFRPDGHIRUPDomR(pGHQRPLQDGRPyGXORGH
SHUGD $VVLP XP PDWHULDO YLVFRHOiVWLFR VHUi FDUDFWHUL]DGR SRU GRLV YDORUHV GH
PyGXORR(HR(
0DWHPDWLFDPHQWH p FRPXP UHSUHVHQWDU R PyGXOR GR VLVWHPD (  FRPR XP
Q~PHURFRPSOH[RFRPSRVWRSHODVGXDVFRPSRQHQWHV
E* = E + iE (11.20)
RQGHDSDUWHUHDOGRQ~PHURFRPSOH[RFRQVWLWXLVHGRPyGXORGHDUPD]HQDPHQWRH
DSDUWHLPDJLQiULDGRPyGXORGHSHUGD
$UD]mRHQWUHRVYDORUHVGHPyGXORGHSHUGD(HPyGXORGHDUPD]HQDPHQWR
(GHILQHXPDJUDQGH]DGHQRPLQDGDWDQJHQWHGHSHUGDWDQLVWRp
E
tan = tangente de perda (11.21)
E
(P RXWUDV SDODYUDV D WDQJHQWH GH SHUGD WDPEpP GHQRPLQDGD IULFomR LQWHUQD
RX DPRUWHFLPHQWR p D UD]mR HQWUH D HQHUJLD GLVVLSDGD SRU FLFOR H D HQHUJLD
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&DUDFWHUL]DomRGH3ROtPHURV 
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11.4.2 Instrumentao
([LVWHP KRMH QR PHUFDGR GLYHUVRV HTXLSDPHQWRV FRPHUFLDLV FRP FDUDFWHUtVWLFDV
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2V PpWRGRV GLQkPLFRPHFkQLFRV VmR PXLWR VHQVtYHLV jV WUDQVIRUPDo}HV RX
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D

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R& (QTXDQWR TXH PRYLPHQWRV PDLV GLVFUHWRV GH UHOD[Do}HV VHFXQGiULDV VmR
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Qual a origem dessas relaxaes secundrias, uma vez que a cadeia como
um todo se encontra sem mobilidade?
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11.4.4 Utilizao da Equao de Arrhenius
&RPR Mi PHQFLRQDGR QR LQtFLR GHVWH FDStWXOR R YDORU GD WUDQVLomR REVHUYDGD QR
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SEquao de WLF (Williams, Landel, Ferry)


C1 (T T0 )
log aT = (11.23)
C 2 + (T T0 )

RQGH& %IJ %pXPDFRQVWDQWHHIJpRYROXPHOLYUHIUDFLRQDOQD7J H& 


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SEquao de Arrhenius
aT = exp H / R (1 / T 1 / T0 ) (11.24)

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DOLQKDGRVFRPRFDPSRHOpWULFR
 2 IDWRU GH SHUGD  WDPEpP GHQRPLQDGR GH FRQVWDQWH GLHOpWULFD GH SHUGD p
SURSRUFLRQDOjFRQGXWkQFLDTXHpDHQHUJLDUHTXHULGDSDUDDOLQKDURVGLSRORVH
PRYHU RV tRQV &RPR R PRYLPHQWR PROHFXODU HP XP SROtPHUR DEDL[R GD 7J p
LQVLJQLILFDQWH TXDQGR R PDWHULDO HVWi QR HVWDGR YtWUHR  UHSUHVHQWD DSHQDV D
HQHUJLD UHTXHULGD SDUD DOLQKDU GLSRORV $FLPD GD 7J  HVWi UHODFLRQDGR j
FRQGXWLYLGDGHL{QLFDSHODIUHTrQFLD
 $FRQGXWLYLGDGHL{QLFDSRGHHVWDUUHODFLRQDGDjYLVFRVLGDGHeHVSHFLDOPHQWH~WLO
SDUDDQDOLVDUSURFHVVRGHFXUDHPPDWHULDLVWHUPRUUtJLGRV
 2 IDWRU GH GLVVLSDomR p H[SUHVVR FRPR WDQ GHOWD   H p DQiORJR j WDQ GHOWD
PHFkQLFDREWLGDSHOR'07$

8PD YH] GHILQLGDV DV SURSULHGDGHV SRGHP VHU IHLWDV DOJXPDV REVHUYDo}HV
DGLFLRQDLV
SRSURGXWRWDQpGLUHWDPHQWHSURSRUFLRQDOjSHUGDGLHOpWULFDGDHQHUJLD
SRIDWRUGHGLVVLSDomRpXPDPHGLGDGDVSHUGDVGLVVLSDGDVVREDIRUPDGHFDORU
SHODVPROpFXODVGRSROtPHURFRPRUHVXOWDGRGDSRODUL]DomRGLHOpWULFDTXDQGRR
PHVPRpH[SRVWRDXPFDPSRHOpWULFR
SDVSHUGDVGLHOpWULFDVQRVGLHOpWULFRVSROLPpULFRVSUHFLVDPVHUFRQVLGHUDGDV
HP FRQH[mR FRP VXD HVWUXWXUD PROHFXODU H HP SDUWLFXODU HPUHODomRj
HVWUXWXUDGDXQLGDGHUHSHWLWLYD
SD SUHVHQoD GH DGLWLYRV FRPR DQWLR[LGDQWHV H RXWURV IDWRUHV FRPR GHJUDGDomR
WpUPLFDR[LGDomRFXUDLQFRPSOHWDHXPLGDGHSRGHPDXPHQWDURYDORUGHWDQ

([LVWH D GHSHQGrQFLD GD UHVSRVWD GLHOpWULFD FRP R WHPSR FRP D IUHTrQFLD GR
FDPSRHOpWULFRHFRPDWHPSHUDWXUD,VWRWHPVLGRPRVWUDGRSRUPHLRGHPRGHORV
TXH GHVFUHYHP RV SURFHVVRV DW{PLFRV H PROHFXODUHV GD SRODUL]DomR QDV PROpFXODV
GRVSROtPHURV
$VIUHTrQFLDVXVDGDVQDVPHGLGDVWrPTXHHVWDUQDIDL[DRQGHDSRODUL]DomRGH
RULHQWDomR GRV GLSRORV QR SROtPHUR VHMD DWLYD (VWDV IUHTrQFLDV VmR PXLWR PDLV
DOWDV GR TXH DTXHODV XVDGDV QRUPDOPHQWH SDUD R '07$ H WLSLFDPHQWH FDHP QD
IDL[DGH+]DN+]$SHVDUGDYDULiYHOSULQFLSDOVHUDWHPSHUDWXUDRVIDWRUHV
H SRGHPVHUHVWXGDGRVFRPRXPDIXQomRGDIUHTrQFLDDQJXODU HQDUHJLmR
GHIUHTrQFLDRQGHH[LVWHXPDUHOD[DomRHGHFUHVFHFRPRPRVWUDD)LJXUD$
PDJQLWXGH GHVWH GHFUpVFLPR R   p XPD PHGLGD GD IRUoD GR GLSROR PROHFXODU
HQYROYLGR QD UHOD[DomR RQGH R p D FRQVWDQWH GLHOpWULFD HVWiWLFD UHODFLRQDGD DR
PRPHQWR GLSRODU UHDO GR SROtPHUR H  p D FRQVWDQWH GLHOpWULFD PHGLGD D DOWDV
IUHTrQFLDV

 $QiOLVH'LHOpWULFDRX7HUPRGLHOpWULFD '($RX'(7$ 


)LJXUD5HSUHVHQWDomRHVTXHPiWLFDGRFRPSRUWDPHQWRGRVIDWRUHVGHDUPD]HQDPHQWR  HSHUGD  
FRPRXPDIXQomRGRORJDULWPRGDIUHTrQFLDDQJXODU0RVWUDWDPEpPDWDQJHQWHGHSHUGDGLHOpWULFD
FRPRXPDIXQomRGH

12.2 Comparao entre DMTA e DETA


'DGRV REWLGRV GH PHGLGDV PHFkQLFD H GLHOpWULFD SRGHP VHU UHODFLRQDGRV
TXDOLWDWLYDPHQWH PDV QHP VHPSUH SRGHP VHU UHODFLRQDGRV GH XP PRGR
TXDQWLWDWLYR
$FRQVWDQWHGLHOpWULFD  SRGHVHUFRQVLGHUDGDFRPRHTXLYDOHQWHjFRPSOLkQFLD
PHFkQLFD -  PHOKRU GR TXH DR PyGXOR ,VWR HOXFLGD R IDWR GH TXH WpFQLFDV
PHFkQLFDVPHGHPDKDELOLGDGHGRVLVWHPDGHUHVLVWLUDRPRYLPHQWRHQTXDQWRTXH
DDYDOLDomRGLHOpWULFDpXPDPHGLGDGDFDSDFLGDGHGRVLVWHPDGHPRYLPHQWDUVH(
DLQGDRVJUXSRVHQYROYLGRVWrPTXHVHUGLSRODUHV
8P DVSHFWR LQWHUHVVDQWH p TXH D SHUGD GLHOpWULFD  SDUHFH HVWDU PDLV
LQWLPDPHQWH DVVRFLDGD DR PyGXOR GH SHUGD ( RX *  GR TXH j FRPSOLkQFLD GH
SHUGDTXDQGRRVGDGRVVmRFRPSDUDGRVSDUDRPHVPRVLVWHPD

&DUDFWHUL]DomRGH3ROtPHURV 
$PEDV DV WpFQLFDV UHVSRQGHP GH PRGR VLPLODU D XPD YDULDomR QD IUHTrQFLD
PHGLGD 4XDQGR D IUHTrQFLD p DXPHQWDGD DV WUDQVLo}HV H UHOD[Do}HV TXH VmR
REVHUYDGDVQDDPRVWUDDSDUHFHPDWHPSHUDWXUDVPDLVHOHYDGDV,VWRpLOXVWUDGRQD
)LJXUDTXHPRVWUDXPDDQiOLVHGHSROL WHUHIWDODWRGHHWLOHQR 2SLFRGHSHUGD
UHSUHVHQWDQGRDWUDQVLomRYtWUHDIRLPHGLGRSRU'07$H'(7$DYiULDVIUHTrQFLDV
HQWUH+]HN+]

)LJXUD&RPSDUDomRGDVFXUYDVREWLGDVSRU'07$H'(7$

2Pi[LPRGRSLFR 7Pi[ PRYHVHGHXPDWHPSHUDWXUDGHa& D+] SDUD


a& D  N+]  R TXH VLJQLILFD XP DXPHQWR GH & QXPD YDULDomR GH
IUHTrQFLD GH VHWH RUGHQV GH PDJQLWXGH (VWD YDULDomR DSUR[LPDVH GD QRUPD
SUiWLFD QD TXDO D WHPSHUDWXUD QR Pi[LPR GH XP SLFR GH SHUGD 7Pi[  RX XP
SURFHVVR GH UHOD[DomR  LUi YDULDU GH FHUFD GH & SDUD FDGD GpFDGD GH YDULDomR QD
IUHTrQFLD(VWHWLSRGHPHGLGDSRGHVHUXVDGRSDUDHVWLPDUDHQHUJLDGHDWLYDomR
( GHXPDWUDQVLomRRXSURFHVVRGHUHOD[DomRDWUDYpVGD(TXDomR
E* = d (log )/d (1/Tmx) (12.1)

RQGHpDIUHTrQFLDGDDQiOLVH
$ UHSUHVHQWDomR JUiILFD GD (TXDomR  p PRVWUDGD QD )LJXUD  SDUD R
SURFHVVR GH UHOD[DomR  HP XPD VpULH GH DPRVWUDV GH SROL PHWDFULODWR GH DOTXLOD 

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$PEDV DV WpFQLFDV '07$ H '(7$  IRUDP XVDGDV SDUD D REWHQomR GRV UHVXOWDGRV H
GmRVHSDUDGDPHQWHOLQKDVUHWDVFRPDPHVPDLQFOLQDomR3RUpPRIDWRGHTXHDV
UHWDV QmR VH VREUHS}HP LQGLFD TXH DV PHGLGDV SRGHP QmR VHU H[DWDPHQWH
HTXLYDOHQWHV

)LJXUD*UiILFRGDIUHTrQFLDHPIXQomRGRLQYHUVRGDWHPSHUDWXUDGH7PD[SDUDRSURFHVVRGHUHOD[DomR
QRSROL PHWDFULODWRGHPHWLOD  300$ SROL PHWDFULODWRGHHWLOD  3(0$ HSROL PHWDFULODWRGHWEXWLOD 
3W%0$ 6tPERORVEUDQFRVUHSUHVHQWDPPHGLGDVUHDOL]DGDVSRUPpWRGRGLHOpWULFRHVtPERORVSUHWRVSDUD
PHGLGDVGLQkPLFRPHFkQLFDV

'LIHUHQoDVEiVLFDVQDVDQiOLVHVGH'07$H'(7$VmRFRPSDUDGDVQR4XDGUR
4XDGUR'LIHUHQoDVEiVLFDVQDVDQiOLVHVGH'07$H'(7$

&DUDFWHUtVWLFD '(7$ '07$


0HGHDSURSULHGDGHHPQtYHO
(VFDODGHGHWDOKHVHVWUXWXUDLV QP
PDFURVFySLFR
'HWHFomRGHHVWUXWXUDVHPXPD
$SDUrQFLDGHFRPSOHWD
PLVWXUDFRPGRPtQLRVPXLWR 6,0
PLVFLELOLGDGH
SHTXHQRV
$FRPSDQKDPHQWRGHUHDo}HVTXH
RFRUUHPQRV~OWLPRVHVWiJLRVGH 6,0 12
FXUDGHXPVLVWHPDWHUPRUUtJLGR
3ySDVWDVyOLGRVHOtTXLGRV
8PDPHVPDDPRVWUDSDUDXPD 6yOLGRVHPJHUDO
7LSRGHDPRVWUD 
DPSODIDL[DGH WUDQVLomR /LPLWDo}HVPHFkQLFDV
VyOLGROtTXLGR 
7RPDGDGHIUHTrQFLDQDIDL[DGH
GpFDGDV GpFDGDV
D+]

&DUDFWHUL]DomRGH3ROtPHURV 
12.3 O equipamento
2LQVWUXPHQWREiVLFRFRQVLVWHGHXPIRUQRFRPXPSRUWDDPRVWUDGHIiFLOOLPSH]D
SDUD SUHYHQLU VXMHLUD H GDQRV QR IRUQR 8P VHQVRU p SRVLFLRQDGR HP XP
FRPSDUWLPHQWRHPEDL[RGRIRUQR([LVWHPTXDWURWLSRVGHVHQVRUHVRVTXDLVHVWmR
UHODFLRQDGRVDVHJXLU
S6HQVRUHPSODFDVFHUkPLFDVSDUDOHODV
S6HQVRUHPFHUkPLFDSDUDILOPHILQR
S6HQVRUHPFHUkPLFDSDUDVXSHUItFLH~QLFD
S6HQVRUUHPRWRSDUDVXSHUItFLH~QLFD FRQILJXUDomRGRWLSRSHQWHGHHOHWURGRV 
2V VHQVRUHV GH SODFDV SDUDOHODV VmR XWLOL]DGRV SDUD PHGLU SURSULHGDGHV GR
LQWHULRU GD DPRVWUD H PRQLWRUDU UHOD[Do}HV PROHFXODUHV 6HQVRUHV GH VXSHUItFLH
VLPSOHVVmRXVDGRVSDUDDYDOLDUSURSULHGDGHVGHVXSHUItFLHHH[SHULPHQWRVGHFXUD
$VDPRVWUDVVmRFRORFDGDVGLUHWDPHQWHQDEDVHGRHOHWURGR1RPRGRGHVXSHUItFLH
VLPSOHV p DSOLFDGD SUHVVmR GLUHWDPHQWH VREUH D DPRVWUD 8P rPEROR FLOtQGULFR
FRQHFWDGR DR /9'7 /LQHDU 9DULDWLRQ 'LIIHUHQWLDO 7UDQVGXWRU  PHGH D HVSHVVXUD GD
DPRVWUD$DQiOLVHpFRQWURODGDSRUXPSURJUDPDGHFRPSXWDGRURSHUDFLRQDOHXVD
DHQWUDGDDSDUWLUGRWUDQVGXWRUGHIRUoDHGR/9'7SDUDPRQLWRUDUDIRUoDDSOLFDGD
HDHVSHVVXUDGDDPRVWUD2HTXLSDPHQWRRSHUDQDIDL[DGHWHPSHUDWXUDGHD
& 
12.4 Exemplos de aplicaes
12.4.1 Identificao de transies
&RPR R '(7$ UHVROYH D UHVSRVWD GH XP SROtPHUR HP VXDV FRPSRQHQWHV GH
DUPD]HQDPHQWR H GH SHUGD VLPLODU DR '07$  HOH p XPD IHUUDPHQWD YDOLRVD SDUD
LGHQWLILFDU WUDQVLo}HV HP SROtPHURV 3RU FDXVD GD DPSOD IDL[D GH IUHTrQFLD
GLVSRQtYHO R '(7$ SRGH RIHUHFHU XP QtYHO GH VHQVLELOLGDGH QmR HQFRQWUDGR HP
RXWUDV WpFQLFDV ,GHQWLILFDomR GH WUDQVLo}HV WHP VLGR UHDOL]DGD SDUD GLYHUVDV
PLVWXUDV GH SROtPHURV 2 '(7$ WDPEpP p FDSD] GH LGHQWLILFDU UHOD[Do}HV
VHFXQGiULDVHPSROtPHURVDVTXDLVQmRVmRGHWHFWDGDVSRU'07$
2V SROtPHURV DPRUIRV DSUHVHQWDP GRLV WLSRV GH SHUGDV GLHOpWULFDV 2 SULPHLUR
WLSR GH SHUGD GLHOpWULFD FKDPDGD SHUGD GLSRORVHJPHQWR GV  GHVLJQDGD SHOD OHWUD
HVWiDVVRFLDGRDRHVWDGRERUUDFKRVR DFLPDGD7JGRSROtPHUR 2VHJXQGRWLSR
FKDPDGR SHUGD GLSRORJUXSR GJ  JHUDOPHQWH GHVLJQDGR SHODV OHWUDV JUHJDV   
HWFGHSHQGHQGRGRPHFDQLVPRGHSHUGDpGHYLGRjRULHQWDomRGRVJUXSRVSRODUHV
$V SHUGDV GHVWH WLSR SRGHP RFRUUHU DQWHV GD 7J GR SROtPHUR QR HVWDGR YtWUHR H
GHSRLVGD7JQRHVWDGRERUUDFKRVR
$ RULHQWDomR GLSRODU GRV VHJPHQWRV GD FDGHLD SULQFLSDO GH XP SROtPHUR
JHUDOPHQWH LQGHSHQGH GD RULHQWDomR GLSRODU GRV VXEVWLWXLQWHV GD FDGHLD ODWHUDO
([LVWHXPDDOWDFRUUHODomRHQWUHDVGLIHUHQWHVRULHQWDo}HVGLSRODUHVGRVVHJPHQWRV

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PROHFXODUHV QR SROtPHUR TXH p XPD FRQVHTrQFLD GDV LQWHUDo}HV LQWHU H
LQWUDPROHFXODUHV 4XDQWR PDLRUHV IRUHP HVWDV LQWHUDo}HV DV XQLGDGHV UHSHWLWLYDV
WHUmR PHQRU PRELOLGDGH &RQVHTXHQWHPHQWH PDLV DOWDV VHUmR DV WHPSHUDWXUDV HP
TXH D WDQ  p Pi[LPD H PDLRUHV VHUmR RV WHPSRV GH UHOD[DomR $VVLP D SHUGD
GLHOpWULFD QRV SROtPHURV H VHX WHPSR GH UHOD[DomR PDLV SURYiYHO GHSHQGHP GD
FRQVWLWXLomR TXtPLFD GD XQLGDGH FRQVWLWXFLRQDO UHSHWLWLYD GD FDGHLD VHQGR
LPSRUWDQWHRQ~PHURGHJUXSRVSRODUHVDQDWXUH]DRWDPDQKRRVIDWRUHVHVWpULFRV
DVLQWHUDo}HVLQWUDHLQWHUPROHFXODUHVHDPRELOLGDGHGDVXQLGDGHV
6H QD FDGHLD SULQFLSDO GR SROtPHUR H[LVWLUHP JUXSRV SRODUHV FDSD]HV GH
RULHQWDUHPVHQRFDPSRHOpWULFRLQGHSHQGHQWHPHQWHXPGRRXWURHDSUHVHQWDUHP
WHPSRVGHUHOD[DomRGLIHUHQWHVQDVFXUYDVGHWDQ YHUVXV7RXGHWDQ YHUVXV 
VHUmRUHJLVWUDGRVGRLVSLFRVPi[LPRVGHSHUGD
$OJXQV DXWRUHV WrP GHPRQVWUDGR D XWLOLGDGH GR '(7$ QD FDUDFWHUL]DomR GH
WUDQVLo}HV TXH RFRUUHP TXDQGR D SROL pWHU pWHU FHWRQD  3((.  SDVVD GR HVWDGR
IXQGLGRSDUDRHVWDGRVyOLGR1HVWHHVWXGRRVYDORUHVGHFRQGXWLYLGDGHL{QLFDIRUDP
LQGHSHQGHQWHV GD IUHTrQFLD TXDQGR R SROtPHUR HQFRQWUDYDVH QR HVWDGR IXQGLGR
(QWUHWDQWR TXDQGR R SROtPHUR HQFRQWUDYDVH QR HVWDGR FULVWDOL]DGR H
VXEVHTHQWHPHQWH SDVVRX SHOD WUDQVLomR YtWUHD j PHGLGD TXH IRL UHVIULDGR IRL
REVHUYDGR R DXPHQWR GHVVD GHSHQGrQFLD FRP D IUHTrQFLD $ FULVWDOL]DomR GH XP
PDWHULDO UHVIULDGR UDSLGDPHQWH D SDUWLU GR HVWDGR IXQGLGR WDPEpP IRL GHWHFWDGD
FRPRXPSURFHVVRGHSHQGHQWHGDIUHTrQFLD

12.4.2 Avaliao da borracha natural vulcanizada, contendo negro de fumo


3DUWtFXODVGHQHJURGHIXPRSRVVXHPXPDDOWDFRQGXWLYLGDGHLQWUtQVHFD$LQFOXVmR
GH QHJUR GH IXPR HP XPD ERUUDFKD YXOFDQL]DGD Gi RULJHP D XP FRPSRUWDPHQWR
GLHOpWULFR FRPSOH[R $V SURSULHGDGHV GLHOpWULFDV VXUJHP D SDUWLU GRV VHJXLQWHV
FRPSRQHQWHV D  SHUGD GH GLSROR QRUPDO D SDUWLU GH FDGHLDV GD ERUUDFKD
YXOFDQL]DGD FRP HQ[RIUH E  SHUGDV GH FRQGXWLYLGDGH GHYLGR D FDPLQKRV GH
FRQGXomR GLUHWD GDV SDUWtFXODV GH QHJUR GH IXPR OLJDGDV QD PDWUL] SROLPpULFD F 
SHUGDV GH 0D[ZHOO:DJQHU GHYLGR j FDSDFLGDGH GDV SDUWtFXODV GH QHJUR GH IXPR
FRQGX]LUHP HP XP PHLR ERUUDFKRVR QmRFRQGXWRU G  SHUGDV HVWUXWXUDLV
FDUDWHUL]DGDVSRUXPDSHUGDTXHpLQGHSHQGHQWHGDWHPSHUDWXUDHGDIUHTrQFLDD
XPDGDGDFRPSRVLomRGHQHJURGHIXPR$VSHUGDVGRWLSR G VmRXPDIXQomRGD
HVWUXWXUD UHDO IRUPDGD SHOR QHJUR GH IXPR QD PLVWXUD H GmR RULJHP D XPD
FRQVWDQWHGLHOpWULFDDDOWDIUHTrQFLD TXHpPDLRUGRTXHDFRQVWDQWHGLHOpWULFD
DDOWDIUHTrQFLDGHXPYXOFDQL]DGRFRPHQ[RIUHVHPDSUHVHQoDGRQHJURGHIXPR
$VSURSULHGDGHVGLHOpWULFDVGHERUUDFKDYXOFDQL]DGDFRPHQ[RIUHFRQWHQGRQHJUR
GHIXPRWrPVLGRHVWXGDGDVSRUPXLWRVSHVTXLVDGRUHV2VUHVXOWDGRVGHUDPRULJHP
D FXUYDV GH  H  FRPR XPD IXQomR GD IUHTrQFLD SDUD YiULDV DPRVWUDV GH

&DUDFWHUL]DomRGH3ROtPHURV 
YXOFDQL]DGRV$VFXUYDVGHSHUGDH[LELUDPGRLVPi[LPRVXPDFVHRXWURD
FV$EDL[DVIUHTrQFLDVDSHUGDDXPHQWRXUDSLGDPHQWHFRPDGLPLQXLomRGD
IUHTrQFLD $ PDLV DOWDV IUHTrQFLDV R Pi[LPR GH SHUGD IRL GHYLGR j RULHQWDomR
GLSRODU D PDLV EDL[DV IUHTrQFLDV R Pi[LPR IRL GHYLGR j SRODUL]DomR GH 0D[ZHOO
:DJQHU H D EDL[D IUHTrQFLD VXUJH XPD SHUGD GHYLGR j FRQGXomR GH FRUUHQWH QD
DPRVWUD)RLREVHUYDGRTXHDPDLVDOWDIUHTrQFLDDFRQVWDQWHGLHOpWULFDSDUDXP
QHRSUHQHWUDWDGR SROLFORURSUHQR IRLGHHQTXDQWRTXHHSDUDDERUUDFKDSXUD
IRLGH(VWHFRPSRUWDPHQWRIRLDWULEXtGRDIDWRUHVHVWUXWXUDLV
8PHVWXGRPDLVFXLGDGRVRGDGHSHQGrQFLDGH H FRPDIUHTrQFLDHFRPD
WHPSHUDWXUD PRVWURX TXH XPD UHJLmR GH SHUGD DGLFLRQDO SRGHULD VHU UHVROYLGD D
TXDOIRLLQGHSHQGHQWHGDIUHTrQFLDHGDWHPSHUDWXUDPHGLGDTXHRWHRUGHQHJUR
GH IXPR QD ERUUDFKD QDWXUDO YXOFDQL]DGD IRL DXPHQWDGR HVWD UHJLmR GH SHUGD
DXPHQWRX7DOUHJLmRGHSHUGDpFRQKHFLGDFRPRDSHUGDHVWUXWXUDOXPDYH]TXH
VXDPDJQLWXGHGHSHQGHQmRDSHQDVGDTXDQWLGDGHGHQHJURGHIXPRSUHVHQWHPDV
WDPEpPGRWLSRGHQHJURGHIXPRXWLOL]DGR
2EVHUYDQGRVH R KLVWyULFR GD SHUGD HVWUXWXUDO IRL SRVVtYHO DVVRFLDU D
PDJQLWXGHGDSHUGDFRPDHVWUXWXUDRXRHVWDGRGHDJUHJDomRGRQHJURGHIXPRQD
PDWUL] ERUUDFKRVD $V HVWUXWXUDV GR QHJUR GH IXPR VmR GHVWUXtGDV TXDQGR D
ERUUDFKDpLQFKDGDRXHVWLUDGDHIRLHQFRQWUDGRTXHDSHUGDHVWUXWXUDOGLPLQXLX
VLJQLILFDWLYDPHQWHHPDPERVRVFDVRV3RUH[HPSORQHQKXPDSHUGDHVWUXWXUDOIRL
REVHUYDGDDRLQFKDUDERUUDFKDHPVROXomRGHQKHSWDQRDRTXHVXJHUHTXHD
SHUGD HVWUXWXUDO VXUJH GH XPD VpULH GH UHDUUDQMRV GDV SDUWtFXODV GH QHJUR GH
IXPRLVWRpGDIRUPDomRGHXPDVpULHGHPLFURFDSDFLWRUHV

12.4.3 Estudos de cura


$ DQiOLVH GLHOpWULFD SHUPLWH FDUDFWHUL]DU DV DOWHUDo}HV UHROyJLFDV H[SUHVVLYDV TXH
DFRPSDQKDPXPSURFHVVRGHFXUD$VLQIRUPDo}HVREWLGDVSRGHPVHUXVDGDVSDUD
LGHQWLILFDUTXDODPHOKRUWHPSHUDWXUDSDUDDUPD]HQDPHQWRGHXPPDWHULDOHTXDLV
VmR DV FRQGLo}HV DGHTXDGDV SDUD R SURFHVVDPHQWR GH SROtPHURV WHUPRUUtJLGRV
HODVW{PHURV DGHVLYRV UHYHVWLPHQWRV HWF &RPR H[HPSORV SRGHP VHU FLWDGRV
HVWXGRV GH DOWHUDo}HV UHROyJLFDV HP SROLXUHWDQRV SHOR DFRPSDQKDPHQWR GR
SURFHVVRGHFXUDHVWXGRVVREUHIOX[RHFXUDGHDGHVLYRVHFRPSRVLo}HVGHVLOLFRQH
XVDGDVHPLVRODPHQWRHSURWHomRGHFRPSRQHQWHVHOHWU{QLFRV

12.4.4 Identificao da origem da relaxao molecular


2VUHVXOWDGRVGH'07$H'(7$SRGHPVHUXVDGRVGHXPPRGRFRPSOHPHQWDUSDUD
GLVWLQJXLU HQWUH UHOD[Do}HV HQYROYHQGR XQLGDGHV SRODUHV H DSRODUHV UHOD[DQGR QR
VLVWHPDSROLPpULFR([DPLQDQGRDUHVSRVWDGRSROL WHUHIWDODWRGHHWLOHQR SRU'07$
H '(7$ SRGHP VHU LGHQWLILFDGRV GRLV SLFRV GH SHUGD SULQFLSDLV HP FDGD XPD GDV

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DQiOLVHV )LJXUD    2 SLFR GH SHUGD D PDLV DOWD WHPSHUDWXUD SLFR  HVWi
UHODFLRQDGRDRSURFHVVRGHWUDQVLomRYtWUHD LVWRpFRQILUPDGRSRUPHGLGDVGH'6& 
2RXWURSLFR UHOD[DomR TXHDSDUHFHDWHPSHUDWXUDPDLVEDL[DVXJHUHTXHH[LVWH
XP SURFHVVR GH UHOD[DomR DWLYR QR HVWDGR YtWUHR 1mR p LPHGLDWDPHQWH yEYLR TXDO
JUXSR p UHVSRQViYHO SRU WDO SURFHVVR PDV HOH p DWLYR HP WHUPRV PHFkQLFRV H
GLHOpWULFRV 8P H[DPH GD HVWUXWXUD GR SROtPHUR VXJHUH TXH D UHOD[DomR QR VyOLGR
YtWUHR SRGHULD HQYROYHU RVFLODomR GR JUXSR IHQLOD PRYLPHQWR GD XQLGDGH
R[LFDUERQLODRXUHDUUDQMRGDXQLGDGH 2&&2 

3ROL WHUHIWDODWRGHHWLOHQR 

1RHVSHFWURGD)LJXUDSRGHVHUREVHUYDGRTXHDLQWHQVLGDGHGRSLFR HP
UHODomR D GR SLFR  p PXLWR PDLV IRUWH QD UHVSRVWD GLHOpWULFD GR TXH QD PHGLGD
PHFkQLFD,VWRVXJHUHTXHRJUXSRTXHHVWiVRIUHQGRUHOD[DomRHVWiDVVRFLDGRFRP
XP PRPHQWR GH GLSROR H HQWmR D RVFLODomR GR JUXSR IHQLOD p DFHLWiYHO FRPR XP
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 &DUDFWHUL]DomRGH3ROtPHURV
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SHUPLVVLYLGDGHGLHOpWULFD
SHVRPROHFXODUQXPpULFRPpGLR
SHVRPROHFXODUSRQGHUDOPpGLR
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SROLPHUL]DomRHPFDGHLD
SROLPHUL]DomRHPHWDSDV
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SROtPHURVGHFRQGHQVDomR
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SUHVVmRRVPyWLFD
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YLVFRHODVWLFLGDGH
YLVFRVLGDGHDEVROXWD
YLVFRVLGDGHHVSHFtILFD
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YLVFRVLGDGHLQWUtQVHFD
YLVFRVLGDGHQHZWRQLDQD
YLVFRVLGDGHUHGX]LGD
YLVFRVLGDGHUHODWLYD
YLVFRVLPHWULD
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YLVFRVtPHWUR8EEHORKGH
YRODWLOL]DomR
YROWDJHPVHQRLGDO
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 &DUDFWHUL]DomRGH3ROtPHURV