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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
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Cidade Universitria Ilha do Fundo
Cep 21.945-970
Rio de Janeiro Brasil
CNPJ 03.484.075/0001-83
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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 SROLDFULODWR 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

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
$UTXLWHWXUDGDPROpFXOD
'HVLJQDomRGR
SROtPHUR
'HILQLomR
/LQHDU
)RUPDGRSHODVOLJDo}HVGRV
PRQ{PHURVHPXP
FRPSULPHQWRFRQWtQXR
5DPLILFDGRWLSR$
$UTXLWHWXUDWLSRSHQWHFRP
UDPLILFDo}HVORQJDV
5DPLILFDGRWLSR%
$UTXLWHWXUDWLSRSHQWHFRP
UDPLILFDo}HVFXUWDV
5DPLILFDGRWLSR&
(VWUXWXUDGHQGUtWLFDQD
TXDODVUDPLILFDo}HV
WDPEpPDSUHVHQWDP
UDPLILFDo}HV
5HWLFXODGR
(VWUXWXUDVQDVTXDLVDV
FDGHLDVSROLPpULFDVHVWmR
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

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

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
HVWDUGLVSRVWRVQRHVSDoRXQVHPUHODomRDRVRXWURVGHPDQHLUDVFRQILJXUDo}HV

GLIHUHQWHV,VWRpSRGHPVHUIRUPDGRVWUrVWLSRVGHDUUDQMRVGLVWLQWRVRVTXDLVVy
SRGHPVHUDOWHUDGRVSHODTXHEUDGHOLJDo}HVTXtPLFDV(VWHVDUUDQMRVUHFHEHUDPR
QRPH GH LVRWiWLFR VLQGLRWiWLFR H DWiWLFR RX KHWHURWiWLFR VHQGR PRVWUDGRV QR
4XDGUR
4XDGUR&ODVVLILFDomRTXDQWRDRDUUDQMRGRViWRPRV
(VWUXWXUD
'HVLJQDomR
'HILQLomR
,VRWiWLFR
7RGRVRVDWRPRVGH
FDUERQRDVVLPpWULFRJH
UDGRVSRVVXHPD
PHVPDFRQILJXUDomR.
$PROpFXODDSUHVHQWD
DOWHUQkQFLDGHFRQIL
6LQGLRWiWLFR JXUDomRGRViWRPRVGH
FDUERQRDVVLPpWULFRV
JHUDGRV
1mRKiRUGHPQD
$WiWLFR
VHTrQFLDGH
FRQILJXUDomRGRV
RX
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

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
SROtPHUR

3ROLDPLGD
/LJDomR
FDUDFWHUtVWLFD
H2N-R-N2H + HO2 C-R-CO2H

H-(NH-R- HCO-R-CO-)nOH + H2O
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
VHGD
Polmeros de polipeptdeos que ocorrem naturalmente

H-(NH-R-CONH-R-CO-)nOH + H2O
H2N-R-CO2H + H2N-R-CO2H

3ROLpVWHU
&HOXORVH
(VWUXWXUDGRSROtPHURUHVXOWDQWH
HO-R-OH + HO2 C-R-CO2H

H-(O-R-OCO-R-CO-)nOH + H2O
HO-R-OH + RO2C-R-CO2R
H-(O-R-OCO-R-CO-)n Cl + ROH
HO-R-CO2H H-(O-R-CO-)nOH + H2O
OC
Ocorre naturalmente
-(C6H12O4-)n - + H2O C6H12O6

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)nRQGH5SRGHVHUTXDOTXHUJUXSRVXEVWLWXLQWHWDLVFRPRKLGURJrQLRDOTXLODDULOD

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
3ROLFORUHWRGHYLQLOD
3ROLHVWLUHQR
3ROLPHWDFULODWRGH
PHWLOD
3ROLLVRSUHQR

&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

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
FRPRSROLy[LGRGHSURSLOHQR

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

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&XUYDVGHWHQVmRYHUVXVGHIRUPDomRYVWtSLFDVSDUDXPSOiVWLFRUtJLGRXPDILEUDXP
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

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 SROLPHWDFULODWR 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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1.3 Nomenclatura de polmeros

3DUDILQDOL]DUHVWDSHTXHQDLQWURGXomRVHUiIHLWDXPDDERUGDJHPUHVXPLGDVREUH
QRPHQFODWXUDGHSROtPHURV

([LVWHPTXDWURWLSRVEiVLFRVGHQRPHQFODWXUDGHSROtPHURV
S1RPHQFODWXUD EDVHDGD QRV PRQ{PHURV 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
SROLPHWDFULODWRGHPHWLODSROLFORUHWRGHYLQLODHSROLy[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
IRUPDGRRSROLiFLGRDPLQROiXULFR
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
SRULVVRRQRPHGRSROtPHURUHVXOWDQWHVHUiSROLWHUHIWDODWRGHHWLOHQR
1RWH TXH HP WRGRV RV FDVRV QRPHV FRPSRVWRV VHPSUH ILJXUDP HQWUH
SDUrQWHVHV

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 SROLHVWLUHQRFRPHWDFULODWR GH PHWLOD SROLHWLOHQRDOWPRQy[LGR
GH FDUERQR SROLPHWDFULODWR GH PHWLODEDOIDPHWLOHVWLUHQR H SROLPHWDFULODWR 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

4XDGUR1RPHQFODWXUDGHDOJXQVSROtPHURVPDLVFRPXQV
1RPH,83$&
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3ROLPHWLOHQR
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SNomes comerciais
2VQRPHVFRPHUFLDLVGHYHPVHUHYLWDGRVXPDYH]TXHXPSROtPHURFRQVWLWXtGRGD
PHVPD HVWUXWXUD TXtPLFD SRGH DSUHVHQWDU QRPHV GLIHUHQWHV XWLOL]DGRV SRU
GLIHUHQWHVIDEULFDQWHV$OpPGLVVRDDVVRFLDomRFRPDHVWUXWXUDGRSROtPHURWRUQD
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$SHVDUGRXVRGHQRPHQFODWXUDVFRPHUFLDLVVHUGHVHVWLPXODGRH[LVWHPDOJXQV
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
FDUERQRGRVPRQ{PHURVGHRULJHP
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Q\ORQ p R QRPH FRPHUFLDO GR SROLKH[DPHWLOHQR VHEDFDPLGD e SRVVtYHO
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PHWLOrQLFRV GD SRUomR GLDPLQD H R VHJXQGR R Q~PHUR GH iWRPRV GH FDUERQR QD
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FDSUyLFR 1HVWH FDVR D SROLDPLGD IRUPDGD IRL RULXQGD GH VRPHQWH XP WLSR GH
PRQ{PHURRTXDOSRVVXLVHLViWRPRVGHFDUERQRHPVXDHVWUXWXUD

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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

8PDVROXomRpFDUDFWHUL]DGDSHORVVHJXLQWHVSDUkPHWURVWHUPRGLQkPLFRV
YROXPH9HQHUJLDLQWHUQD8HQWURSLD6HQHUJLDOLYUHGH*LEEV*HQWDOSLD+HWF
1RFDVRGHXPSURFHVVRHPVROXomRFRVWXPDVHGHWHUPLQDUDGLIHUHQoDHQWUHDV
IXQo}HVWHUPRGLQkPLFDVGDVROXomRHDVPHVPDVIXQo}HVGRVFRPSRQHQWHVSXURV
DQWHV GD GLVVROXomR $ YDULDomR GD HQHUJLD OLYUH GH PLVWXUD *P p SRUWDQWR D
GLIHUHQoDHQWUHDHQHUJLDOLYUHGDVROXomR*VROHRVRPDWyULRGDVHQHUJLDVOLYUHVGRV
FRPSRQHQWHVGDPLVWXUD*FRPS
Gm = Gsol - Gcomp
(energia livre de mistura)
(2.1)
(PXPDVROXomRLGHDODPHGLGDTXDQWLWDWLYDGHXPSDUkPHWURWHUPRGLQkPLFR
GHXPDVROXomR*86HWFSRGHVHUFRQVLGHUDGDFRPRDVRPDGDVUHVSHFWLYDV
TXDQWLGDGHVWHUPRGLQkPLFDVGHVHXVFRPSRQHQWHVOHYDQGRVHHPFRQWDDIUDomR
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

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T , P, n
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(VWDV PXGDQoDV TXDQGR UHODFLRQDGDV D PRO GR FRPSRQHQWH DGLFLRQDGR VmR
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SDUFLDOPRODU*L
n
i
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;
p ,T ,
nj
S =
ni
p ,T ,
nj
n
i

Gi =
p ,T ,
nj
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SDUFLDOPRODU
G = =
ni
i
(2.5)
p ,T ,
nj
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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
FRPSRQHQWHVGRVLVWHPDSRGHVHUUHSUHVHQWDGDSHODH[SUHVVmR
Z =Z1n1 + Z2n2 + Z3n3 +...
(2.8)
RQGH=pXPDIXQomRWHUPRGLQkPLFDH[WHQVLYDYROXPHHQWDOSLDHQWURSLDHWFH

=LpDIXQomRSDUFLDOPRODUFRUUHVSRQGHQWH

2.2 Soluo ideal e solues reais

2FRPSRUWDPHQWRGHVLVWHPDVIRUPDGRVSRUPDFURPROpFXODVSRGHVHUGHVFULWRGH
IRUPD VLPSOLILFDGD FRPR XP FRQMXQWR IRUPDGR SRU GRLV FRPSRQHQWHV 4XDQGR
XPDSHTXHQDTXDQWLGDGHGHSROtPHURFRPSRQHQWHpGLVVROYLGDHPXPVROYHQWH
TXDOTXHU FRPSRQHQWH DV LQWHUDo}HV HQWUH RV FRPSRQHQWHV GHSHQGHP GD
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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

RXVHMDVyGHSHQGHGDIUDomRPRODUGRFRPSRQHQWHLx LQDVROXomR
$IUDomRPRODUSDUDVROXo}HVLGHDLVpUHODFLRQDGDjSUHVVmRGHYDSRUSRUPHLR
GHXPDH[SUHVVmRHPStULFDFRQKHFLGDFRPROHLGH5DRXOW(TXDomR
xi = pi/pio
(2.12)
RQGHSLpDSUHVVmRGHYDSRUGRFRPSRQHQWHLQDVROXomRHSLRpDSUHVVmRGHYDSRU
GRFRPSRQHQWHLSXUR
6H R FRPSRUWDPHQWR GD VROXomR QmR VHJXH D OHL GH 5DRXOW D VROXomR p
GHQRPLQDGD VROXomR QmRLGHDO RX VROXomR UHDO e R TXH DFRQWHFH FRP D PDLRU
SDUWHGRVVLVWHPDV
6H D UD]mR SLSLR IRU FRORFDGD HP JUiILFR HP IXQomR GHx L WUrV VLWXDo}HV GLVWLQWDV
SRGHPVHUREVHUYDGDVGHSHQGHQGRGDQDWXUH]DGRVLVWHPD(VWDVVLWXDo}HVHVWmR
LOXVWUDGDVQD)LJXUDRQGHSHSVmRUHVSHFWLYDPHQWHDVSUHVV}HVGHYDSRUGR
VROYHQWHSXURHQDVROXomRH[pDIUDomRPRODUGRSROtPHURQDVROXomR
)LJXUD'HSHQGrQFLDGDSUHVVmRGHYDSRUFRPDFRPSRVLomRGDVROXomR$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

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
= G i = RT ln
i
pi
o
pi
(2.17)
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

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

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

(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

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

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
XPJUXSRDFtGLFRGRDGRUGHSUyWRQVLVWRpKLGUR[LODFDUER[LODDPLQDHWF2
RXWUR JUXSR WHP TXH VHU EiVLFR DFHSWRU GH SUyWRQV LVWR p R[LJrQLR
FDUERQLODVKLGUR[LODVpWHUHVQLWURJrQLRDPLQDVHDPLGDVHKDORJrQLRVIO~RU
HFORUR6mRLQFOXtGDVQDVIRUoDVGRWLSRiFLGREDVHRXIRUoDVGH/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

2FDVRPDLVVLPSOHVpDTXHOHRQGHDVVROXo}HVH[LEHPVRPHQWHLQWHUDo}HVGR
WLSRYDQGHU:DDOV6HRVOtTXLGRVVmRDSRODUHVRXVHMDRPRPHQWRGLSRODUp]HUR
VyH[LVWHPIRUoDVGHGLVSHUVmRHQWUHHOHV8VXDOPHQWHHVWHVOtTXLGRVVHPLVWXUDP
EHP HP XPD ODUJD IDL[D GH WHPSHUDWXUD 3RU H[HPSOR SROLKLGURFDUERQHWRV
DPRUIRVDSRODUHVSROLLVREXWLOHQRSROLLVRSUHQRHSROLEXWDGLHQRVHGLVVROYHPEHP
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
SROLDFULORQLWULODQmRVHGLVVROYHPHPVROYHQWHVDSRODUHV
7DEHOD'LVWkQFLDLQWHUDW{PLFDHHQHUJLDGHGLVVRFLDomRHPIXQomRGRWLSRGHOLJDomRHQWUHPROpFXODV
7LSRVGHOLJDomR
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YDQGHU:DDOV
'LVWkQFLD
LQWHUDW{PLFDc

(QHUJLDGHGLVVRFLDomR
.FDOPRO

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

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\ORQSRUH[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
$FRPSRVLomRTXtPLFDGHPXLWRVSROtPHURVGLIHUHGHSHQGHQGRGDVXDFRQGLomRGH
SUHSDUDomR 3RU H[HPSOR DPRVWUDV GLIHUHQWHV GH DFHWDWR GH FHOXORVH SRGHP WHU
GLIHUHQWHVJUDXVGHDFHWLODomR$PRVWUDVGHSROLiOFRROYLQtOLFRSRGHPDSUHVHQWDU
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 SROLWHWUDIOXRURHWLOHQR 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[RSHVRPROHFXODUVROYHQWHSRGHPSHQHWUDUQDIDVHGHSROtPHUR
'HVWD IRUPD XP SROtPHUR UHWLFXODGR SRGH VRIUHU LQFKDPHQWR OLPLWDGR

$XPHQWDQGR D GHQVLGDGH GH UHWLFXODomR D FDSDFLGDGH GH DEVRUomR GH OtTXLGR GH
EDL[R SHVR PROHFXODU GLPLQXL 4XDQGR RV VHJPHQWRV TXH IRUPDP R UHWtFXOR VmR
PXLWRSHTXHQRVRSROtPHURSHUGHFRPSOHWDPHQWHDFDSDFLGDGHGHLQFKDU
2.5.8 Temperatura
(VWH IDWRU p PXLWR LPSRUWDQWH QD GHILQLomR GRV SDUkPHWURV TXH GHILQHP D
VROXELOLGDGH GH XP SROtPHUR TXH SRGH PHOKRUDU RX SLRUDU FRP D YDULDomR GD
WHPSHUDWXUD2VVLVWHPDVSROtPHURVROYHQWHJHUDOPHQWHDSUHVHQWDPGLDJUDPDVGH
IDVH FDUDFWHUtVWLFRV FRP WHPSHUDWXUDV FUtWLFDV ([HPSORV VmR VLVWHPDV SROtPHUR
VROYHQWH TXH DSUHVHQWDP WHPSHUDWXUD FRQVROXWD VXSHULRU 8&67 RX WHPSHUDWXUD
FRPVROXWDLQIHULRU/&67$)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

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
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R
R
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o
(Ei /Vi)
o
(Ei / Vi)
densidade de energia coesiva
(2.18)
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
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7DEHOD3DUkPHWURGHVROXELOLGDGHGHDOJXQVSROtPHURVHVROYHQWHV
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FDOFP

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
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GHFRPSOH[RVVROYDWDGRV
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p GRDGRU JUXSR iFLGR H RXWUR p DFHSWRU GH SUyWRQV JUXSR EiVLFR $ VHJXLU p
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$
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$ FODVVH $ FRQVLVWH GH FRPSRVWRV TXH FRQWpP VRPHQWH GRDGRUHV GH SUyWRQV
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R KLGURJrQLR &+&O &+%U &+&O HWF 2 39& H R SROLFORURSUHQR SHUWHQFHP D
HVWDFODVVH
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FHWRQDV DOGHtGRV pWHUHV pVWHUHV DPLQDV WHUFLiULDV ROHILQDV EHQ]HQR H RXWURV

FRPSRVWRVDURPiWLFRVDFHSWRUHVGHSUyWRQVVmRiWRPRVGRWLSR21H)2SROLWH
WUDIOXRURHWLOHQRRSROLDFHWDWRGHYLQLODHRVSROLDFULODWRVSHUWHQFHPDHVWDFODVVH
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iJXD'HQWUHRVSROtPHURVGHVWDFDPVHRSROLiOFRROYLQtOLFRRSROLiFLGRDFUtOLFR
RSROLiFLGRPHWDFUtOLFRHDVSROLDPLGDV
$ FODVVH 1 FRQVLVWH GH FRPSRVWRVTXH QmR SRVVXHP TXDOTXHU JUXSR FDSD] GH
IRUPDUOLJDomRKLGURJrQLRFRPRKLGURFDUERQHWRVVDWXUDGRV
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WDLVVXEVWkQFLDVRWLSRSULQFLSDOGHLQWHUDomRpGLVSHUVmR
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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 SROLiOFRRO YLQtOLFR SHUWHQFH j FODVVH $% H p FDSD] GH
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GLVVROYHUGHSHQGHGDWHPSHUDWXUD
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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

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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
SGLVWkQFLDH[WUHPRDH[WUHPRTXDGUiWLFDPpGLD
(r 2 )
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

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


( )
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
(2.24)
RQGHQLpRQ~PHURGHLWLSRVGHOLJDomRGHFRPSULPHQWROL
E ,QWHUDo}HV GH ORQJR DOFDQFH VmR LQWHUDo}HV TXH GHSHQGHP GDV LQWHUDo}HV
SROtPHURVROYHQWHHVmRGHWHUPLQDGDVSHORFRHILFLHQWHGHH[SDQVmRHSHOR
SDUkPHWURGHYROXPHH[FOXtGR](VWHVSDUkPHWURVVmRFRUUHODFLRQDGRVDSDUWLU
GDVHJXLQWHHTXDomR
x
te
=
z
c
lim
x

(2.25)
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
XPGHWHUPLQDGRVROYHQWHGLPHQV}HVSHUWXUEDGDVHHPVROYHQWHWHWDGLPHQV}HV
QmRSHUWXUEDGDVDXPDWHPSHUDWXUDHVSHFtILFD
(r )
=
a
(r )
2 1 2
2 1 2
0
(s )
=
(s )
2 1 2
2 1 2
0
(2.26)
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
soL
(2.27)
$ GHWHUPLQDomR GH GLPHQV}HV QmRSHUWXUEDGDV SRGH VHU IHLWD D SDUWLU GH

WpFQLFDV FRPR YLVFRVLGDGH H HVSDOKDPHQWR GH OX] GH VROXo}HV GLOXtGDV GH
SROtPHURVDVTXDLVVHUmRGLVFXWLGDVHPFDStWXORVSRVWHULRUHV

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
6RQ/WG*ODVJRZ
<RUN
0DQR ( % H 0HQGHV / & ,QWURGXomR D 3ROtPHURV D HG (GLWRUD (GJDUG
%OXFKHU/WGD6mR3DXOR
0RRUH : - )tVLFR4XtPLFD 6mR 3DXOR $R /LYUR 7pFQLFR 6$ 7UDGHP
SRUWXJXrV
1HZ<RUN
9DQ.UHYHOHQ':H+RIW\]HU3-3URSHUWLHVRI3RO\PHUV(OVHYLHU3XEOLVKLQJ
&RPSDQ\$PVWHUGDP

&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)

)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
0pGLDVEDVHDGDVQDIUDomRHPSHVRZLGDVPROpFXODVGHXPGHWHUPLQDGRSHVR
PROHFXODU 0L FRQGX]HP j GHILQLomR GH SHVR PROHFXODU SRQGHUDO PpGLR M Z
GHVFULWDDVHJXLU
wi Mi N i Mi2
=
Mw =
wi
N i Mi
(3.2)
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
Mv =
1+
Ni Mi
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

)LJXUD(IHLWRGDDGLomRGHSHTXHQDTXDQWLGDGHGHPDFURPROpFXODVGHEDL[R&RXDOWR%SHVR

PROHFXODUQRVYDORUHVGH
M ZH M Q
$ GLVWULEXLomR GH SHVR PROHFXODU RX SROLGLVSHUVmR p GHWHUPLQDGD D SDUWLU GD

UD]mR 0 Z 0 Q 3DUD DPRVWUDV PRQRGLVSHUVDV RV YDORUHV GH 0 Q H 0 Z VmR
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 Z 0pWRGRV TXH UHTXHUHP FDOLEUDomR LQFOXHP PHGLGDV GH
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


7DEHOD0pWRGRVXWLOL]DGRVSDUDGHWHUPLQDomRGRSHVRPROHFXODUGHSROtPHURV
$QiOLVHGHJUXSRWHUPLQDO
$ $EVROXWR
5 5HODWLYR
$
(EXOLRVFRSLDHFULRVFRSLD
$
0 Q
3UHVVmRRVPyWLFD
$
0 Q
$
0 Q
(VSDOKDPHQWRGHOX]
$
0 Z
$
0 Z
8OWUDFHQWULILJDomR
$
0 Z
9LVFRVLGDGH
5
0 Y
5
0 QH 0 Z
0pWRGR
(VSDOKDPHQWRGHUDLRV;DEDL[R
kQJXOR
&URPDWRJUDILDGHH[FOXVmRSRU
WDPDQKR
3HVRPROHFXODU
0 Q
$OJXQVDXWRUHVFRQVLGHUDPHVWHPpWRGRUHODWLYR

81(6&26DQWLDJR
1HZ<RUN
6RQ/WG*ODVJRZ
<RUN
1HZ<RUN

&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
SHVRPROHFXODUSRLVQHVWHFDVRDFRQFHQWUDomRGHJUXSRVWHUPLQDLVpDOWD
(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
SROLFRQGHQVDomRRXDLQGDDIRUPDomRGHJUXSRVIXQFLRQDLVSRUUDPLILFDomR
(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

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
VROXomRGHDQLGULGRDFpWLFRHPSLULGLQDHPYROXPH
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

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
Q + Q
(4.5)
3DUD VROXo}HV PXLWR GLOXtGDV (n1 + n2 ) p SUDWLFDPHQWH LJXDO D n1 Q~PHUR GH

PROHVGRVROYHQWH(QWmR
x2 = n2
n1
(4.6)
RQGH x1 pDIUDomRPRODUGRVROYHQWHQDVROXomRH n1 H n2 VmRUHVSHFWLYDPHQWHR

Q~PHURGHPROHVGRVROYHQWHHGRVROXWRQDVROXomR
3RURXWURODGRRYROXPHGDVROXomRSRGHVHUGHILQLGRFRPR
V = V1o n1
(4.7)
RQGH9pRYROXPHGDVROXomR9RpRYROXPHSDUFLDOPRODUGRVROYHQWHQDVROXomRH
QpRQ~PHURGHPROHVGRVROYHQWHQDVROXomR

6DEHVHDLQGDTXHRQ~PHURGHPROHVpLJXDOjUD]mRHQWUHDPDVVDHPJUDPD
HRSHVRPROHFXODU(TXDomR
n2 = m
(4.8)
RQGHPpDPDVVDGRVROXWRSROtPHURHPJUDPDVH0pRVHXSHVRPROHFXODU

&RPELQDQGR DV (TXDo}HV H D IUDomR PRODU GR VROXWR SROtPHUR QD
VROXomRSRGHVHUGHILQLGDFRPR
[ =
0 = P 9
9
9 0
R
(4.9)
9
&RPRDUD]mRP9pDFRQFHQWUDomRGRSROtPHURFHPJP/DIUDomRPRODU[
SRGHVHUUHHVFULWDFRPR
[ =
F 9 R
0
(4.10)
$UHODomRHQWUHRSRWHQFLDOTXtPLFRGDPLVWXUDHDIUDomRPRODUGRSROtPHURQD
VROXomR(TXDomRSRGHHQWmRVHUHVFULWDFRPR
2
c 2V10
c V 0
0
2 1
+
+
1 1 = RT
2
M
(4.11)
RX
1 10 = RTc 2V10 + Ac 2 + Bc 22 +
M
(4.12)
RQGH0$H%VmRGHILQLGRVUHVSHFWLYDPHQWHFRPRRSULPHLURFRHILFLHQWHYLULDOR
VHJXQGRFRHILFLHQWHYLULDOHRWHUFHLURFRHILFLHQWHYLULDO
2SULPHLURFRHILFLHQWHYLULDOFRUUHVSRQGHDRLQYHUVRGRSHVRPROHFXODUQXPpULFR
PpGLR2VHJXQGRFRHILFLHQWHYLULDOHRWHUFHLURFRHILFLHQWHYLULDOIRUQHFHPXPDLGpLD
GDVLQWHUDo}HVHQWUHSROtPHURHVROYHQWHFRPRVHUiGLVFXWLGRSRVWHULRUPHQWH

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
c o c
Mn
(4.13)
RQGHpDSUHVVmRRVPyWLFDHFpDFRQFHQWUDomRGRSROtPHUR
S3DUDRVPRPHWULDGHSUHVVmRGHYDSRU
S 3 9 R
OLP =
0Q
F R F
(4.14)
RQGH SpDGLIHUHQoDGHSUHVVmRGHYDSRUHQWUHVROYHQWHHVROXomR 3 pDSUHVVmR

R
GHYDSRUGRVROYHQWHSXURH9 pRYROXPHPRODUGRVROYHQWH

S3DUDFULRVFRSLD
T f
lim
c 0
c
2
RT f M s 1
=
H M

f
n
(4.15)
RQGH 7IpRDEDL[DPHQWRGRSRQWRGHFRQJHODPHQWR pDGHQVLGDGHGRVROYHQWH

0VpRSHVRPROHFXODUGRVROYHQWH7IpRSRQWRGHFRQJHODPHQWRGRVROYHQWHH+Ip
DYDUDLomRGDHQWDOSLDGHIXVmR

S3DUDHEXOLRVFRSLD
2
T b RT b M s 1
lim
c o
c H b M n
(4.16)
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

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
3URSULHGDGH
3UHVVmRRVPyWLFDFPGHVROYHQWH
$EDL[DPHQWRGDSUHVVmRGHYDSRU
PP+J
'HFUpVFLPRGRSRQWRGH
FRQJHODPHQWRR&
(OHYDomRGRSRQWRGHHEXOLomRR&
6HQVLELOLGDGH
0 Q
0 Q
0 Q

[
[
[
[
[
[
[
[
[
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$SUHVVmRGHYDSRUGRVROYHQWHVREUHDVROXomRSp
VHPSUHPHQRUGRTXHDSUHVVmRGHYDSRUGRVROYHQWHVREUHRVROYHQWHSXURSR
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

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
p1 = p1o . x1
(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)
(QWmR
p1 = p1o (1-x2)
p 1o - p 1 = p 1o.x 2
(4.19)
ou
p = p1o.x2
(4.20)
$ GLIHUHQoD GH SUHVVmR GH YDSRU p UHODFLRQDGD FRP D GLIHUHQoD GH WHPSHUDWXUD
DWUDYpVGDHTXDomRGH&ODXVLXV&ODSH\URQGHVFULWDDVHJXLU
S+Y
S
=
57
7
(4.21)
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
S+Y
(4.22)
&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 =
[
+Y
(4.23)
/HPEUDQGRTXHDIUDomRPRODU[pLJXDODUD]mRHQWUHRQ~PHURGHPROHVGR
VROXWRHGRVROYHQWHQQHTXHRQ~PHURGHPROHVpGHILQLGRFRPRDUD]mR
HQWUHDPDVVDHPJUDPDVHRSHVRPROHFXODUDYDULDomRGDWHPSHUDWXUDSRGHVHU
H[SUHVVDGDVHJXLQWHIRUPD
0
57 Q 57 P
7 =

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

VHU UHODFLRQDGD j FRQFHQWUDomR GD DPRVWUD H DR VHX SHVR PROHFXODU DWUDYpV GD
VHJXLQWHHTXDomR
F
57
7 =
0
0
+ Y
(4.25)
RXVLPSOHVPHQWH
c2
T = K
M2
(4.26)
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
FkPDUDWDPEpPpFRQWURODGDDWUDYpVGHXPVHJXQGREORFRGHDTXHFLPHQWR2V
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

)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

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 +
M
2 M2 2
(4.27)
RX
R 1
=
+ A2 c2 +
Kc2 M 2
(4.28)
&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

)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

7DEHOD3DGU}HVFRPXQVSDUDFDOLEUDomRGHRVP{PHWURGHSUHVVmRGHYDSRU
3DGUmR
0DQLWRO
6XFURVH
%HQ]LOD
%LIHQLOD
3DGU}HVGHSROLHVWLUHQR
6ROXELOLGDGH
JXD
JXD
6ROYHQWHRUJkQLFR
6ROYHQWHRUJkQLFR
6ROYHQWHRUJkQLFR
$QWHVGDDQiOLVHGDVXEVWkQFLDSURSULDPHQWHGLWDGHYHVHSURFHGHUjFDOLEUDomR
GRDSDUHOKRGHWHUPLQDQGRVHDFRQVWDQWH.HRHUURGDPHGLGD
3DUDGHWHUPLQDomRGDFRQVWDQWH.GRDSDUHOKRGHYHPVHID]HUDVPHGLGDVGH5
GDVXEVWkQFLDXVDGDFRPRSDGUmRGHFDOLEUDomREHQ]LODSRUH[HPSORXWLOL]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
GRLVRFWDQRHRYDORUHQFRQWUDGRQDPHGLGD

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

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 DRVYROXPHVVmRLJXDLVSRUpPRSRWHQFLDOTXtPLFR
GRFRPSDUWLPHQWRjGLUHLWDVROYHQWHSXURpPDLRUGRTXHDTXHOHGDHVTXHUGD6HD
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

$YDULDomRGRSRWHQFLDOTXtPLFRFRPDSUHVVmRjWHPSHUDWXUDFRQVWDQWHpGDGD
SHODVHJXLQWHHTXDomR
= V1
(4.31)
= V1p
(4.32)
RX
,QWHJUDQGRWHUHPRV
1
1 =
1
o
V P
(4.33)
1RVH[SHULPHQWRVUHODFLRQDGRVjRVPRPHWULDGHPHPEUDQDRYROXPHpVHPSUH
PDQWLGRFRQVWDQWH(QWmR
1o - 1 = V1o(p po) = V1
(4.34)
1 - 1o = 1 = RTlnx1 = - V1o
(4.35)
RT
= O ln x 1
V1
(4.36)
R

RQGHpDSUHVVmRRVPyWLFDH9 pRYROXPHSDUFLDOPRODUGRVROYHQWHSXUR
&RPELQDQGRVHD(TXDomRFRPD(TXDomRWHPVHTXH
RX
RQGH5pDFRQVWDQWHGRVJDVHVSHUIHLWRVH7pDWHPSHUDWXUDDEVROXWDHP.HOYLQ
&RPR
lnx1 = ln(1-x2) = -x2 x22/2 - ....
(4.37)
RT
= O x2
V1
(4.38)
HQWmR
$IUDomRPRODUGRFRPSRQHQWHpLJXDOD

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
V1O n1
(4.40)
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
V
(4.41)
$ (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
Q
57
Q

+
+
=

Q
9
(4.42)
+ $F + $F +
= 57F
0Q
(4.43)
6DEHQGRVHTXHRQ~PHURGHPROHVpLJXDOjPDVVDGDDPRVWUDHPJUDPDVZ
GLYLGLGDSHORVHXSHVRPROHFXODU0Q Z0HVDEHQGRVHWDPEpPTXHDPDVVD
GD DPRVWUD Z GLYLGLGD SHOR YROXPH GD VROXomR 9 p LJXDO j FRQFHQWUDomR GR
SROtPHURQDVROXomRWHPRV


RXUHDUUDQMDQGR
= 57
+ $F + $F +
F
0Q
(4.44)
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
SROtPHURHPGLIHUHQWHVVROYHQWHV7RGDVDVUHWDVHQFRQWUDPVHQRPHVPRSRQWRQD
RUGHQDGD LQGLFDQGR TXH R YDORU REWLGR GH SHVR PROHFXODU QXPpULFR PpGLR
LQGHSHQGHGRWLSRGHVROYHQWH
)LJXUD'HSHQGrQFLDGHFFRPDFRQFHQWUDomRGHVROXomRGHSROtPHURHPGLIHUHQWHVVROYHQWHV2
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
VROYHQWHERQVVROYHQWHV4XDQGRRFRHILFLHQWHDQJXODUIRULJXDOD]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

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
3ROtPHUR
0 Q [
6ROYHQWH
3ROLHVWLUHQR
3ROLHVWLUHQR
3ROLHVWLUHQR
3ROLLVREXWLOHQR
3ROLLVREXWLOHQR

7ROXHQR
'LFORURHWDQR
&LFORKH[DQR
&LFORKH[DQR
%HQ]HQR
7HPSHUDWXUD
R&

$[
FPPROJ

3DUDXPGHWHUPLQDGRVROYHQWHH[FHWRHPFRQGLo}HVWHWDRYDORUGH$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

)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

$ )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
JDUUDOLJDGDDRGLDIUDJPDPHGHDGHIOH[mRSURPRYLGDSHODSUHVVmRRVPyWLFD
)LJXUD(VTXHPDGHXPRVP{PHWURDXWRPiWLFR
$ FRQILDELOLGDGH GDV PHGLGDV REWLGDV SRU RVPRPHWULD GHSHQGH IXQGDPHQ

WDOPHQWHGDTXDOLGDGHGDPHPEUDQD$PHPEUDQDGHYHVHUSHUPHiYHODRVROYHQWH
H LPSHUPHiYHO DR VROXWR SROtPHUR $ PHPEUDQD QmR SRGH VRIUHU LQFKDPHQWR HP
FRQWDWR FRP R VROYHQWH $ PDLRULD GDV PHPEUDQDV p IHLWD j EDVH GH FHOXORVH
&HOXORVH UHJHQHUDGD FHORIDQH p HPSUHJDGD FRP VROYHQWHV RUJkQLFRV H DFHWDWR GH
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
IHLWDV D YiULDV FRQFHQWUDo}HV QD IDL[D GH D SHVRYROXPH $ GLIHUHQoD GH
SUHVVmRpUHJLVWUDGDGLYLGLGDSHODFRQFHQWUDomRFRUUHVSRQGHQWHHUHODFLRQDGDDHVWD

FRQFHQWUDomR D ILP GH HVWDEHOHFHU D UHODomR F YHUVXV F RX F YHUVXV F $
H[WUDSRODomRjFRQFHQWUDomR]HURLQWHUVHomRQRHL[RGDVRUGHQDGDVIRUQHFHRSHVR
PROHFXODUFRPRLOXVWUDGRQD)LJXUD
1RWUDWDPHQWRGHGDGRVGDSUHVVmRRVPyWLFDpPXLWRLPSRUWDQWHDXWLOL]DomRGH
XQLGDGHVDSURSULDGDV$SUHVVmRRVPyWLFDpGDGDSHOD(TXDomR
= gh
(4.46)
RQGH pDGHQVLGDGHGRVROYHQWHJpDDFHOHUDomRGHYLGRjJUDYLGDGHPVH

K p D SUHVVmR GR VROYHQWH H[SUHVVD HP FHQWtPHWURV $ FRQFHQWUDomR GD VROXomR p
H[SUHVVD HP J/ $ 7DEHOD DSUHVHQWD DV XQLGDGHV GH F FKDPDGD SUHVVmR
RVPyWLFD UHGX]LGD FRQVWDQWH XQLYHUVDO GRV JDVHV 5 H VHJXQGR FRHILFLHQWH YLULDO
QRVVLVWHPDV&*6HLQWHUQDFLRQDO
$ XQLGDGH GR VHJXQGR FRHILFLHQWH YLULDO H[SUHVVD QD 7DEHOD FRUUHVSRQGH j
(TXDomR 6H D GHSHQGrQFLD F YHUVXV F IRU H[SUHVVD GH IRUPD GLIHUHQWH D
XQLGDGH GR VHJXQGR FRHILFLHQWH YLULDO VHUi GLIHUHQWH $ 7DEHOD DSUHVHQWD RV
GLIHUHQWHV PRGRV GH H[SUHVVDU D SUHVVmR RVPyWLFD UHGX]LGD H DV XQLGDGHV GH $
FRUUHVSRQGHQWHV

7DEHOD8QLGDGHVQRUPDOPHQWHXVDGDVSDUDH[SUHVVDUDSUHVVmRRVPyWLFDUHGX]LGDHRVHJXQGR
FRHILFLHQWHYLULDO
3DUkPHWURV
F
5
$
8QLGDGHV
&*6
GLQD/JFP
/DWPPRO.
/PROJ
,QWHUQDFLRQDO
-NJ
-.PRO
PPRONJ

7DEHOD8QLGDGHVGRVHJXQGRFRHILFLHQWHYLULDO$
8QLGDGHGRVHJXQGRFRHILFLHQWHYLULDO$
6LVWHPD&*6
6LVWHPDLQWHUQDFLRQDO
(TXDomR
RT
=
+ A2 c + ....
c Mn
GLQDFPJ
-PNJ
= RT
+ A2 c +
c
Mn
FPPROJ
PPRONJ
RT
(1 + A2 c + )
=
c Mn
FPJ
PNJ
3DUDH[SUHVVDUDSUHVVmRRVPyWLFDHPDWPRVIHUDVDTXDQWLGDGH H[SUHVVDHP
FHQWtPHWURVGDFROXQDGDVROXomRGHYHVHUPXOWLSOLFDGDSHODGHQVLGDGHGRVROYHQWH
FRQVLGHUDGD LJXDO j GHQVLGDGH GD VROXomR GLOXtGD H GLYLGLGD SHOD GHQVLGDGH GR
PHUF~ULRHSRUDWP FP+J6HDFRQFHQWUDomRGDVROXomRIRUH[SUHVVDHP
JP/RQXPHUDGRUGHYHUiVHUPXOWLSOLFDGRSRUSDUDVHREWHUDFRQFHQWUDomR
GDVROXomRHPJ/$GHWHUPLQDomRGRSHVRPROHFXODUSRGHVHUIHLWDXWLOL]DQGRVHD
VHJXLQWHIyUPXOD
Mn =
0,082T 13,6 76 10

1
c 2 c 0
(4.47)
RQGH7pDWHPSHUDWXUDXVDGDQDH[SHULrQFLDHPHVFDOD.HOYLQHpDGHQVLGDGHGR
VROYHQWH
5HVXPLQGRDWpFQLFDDSUHVHQWDDVYDQWDJHQVGHVFULWDVDVHJXLU
S$ WpFQLFD IRUQHFH M n DEVROXWR 1mR Ki QHFHVVLGDGH GH FDOLEUDomR FRP
VXEVWkQFLDVSDGUmR 3DGU}HV VmR HQWUHWDQWR UHFRPHQGDGRV SDUD YHULILFDU R
GHVHPSHQKRGDVPHPEUDQDV
S&RQWDPLQDQWHV GH EDL[R SHVR PROHFXODU WUDoRV GH VROYHQWH UHVLGXDO
DQWLR[LGDQWHVHWFSRGHPVHUWROHUDGRVSRUTXHHOHVVHGLVWULEXHPHPDPERVRV
ODGRVGDPHPEUDQD1RFDVRGDRVPRPHWULDGHSUHVVmRGHYDSRUDSUHVHQoDGH
SHTXHQDSRUomRGHVXEVWkQFLDGHEDL[RSHVRPROHFXODUSRGHFRQGX]LUDYDORUHV
GH M n PDLVEDL[RV

SM n GH FRSROtPHURV HP EORFR RX JUDIWL]DGRV SRGH VHU GHWHUPLQDGR VHP
SUREOHPDV XPD YH] TXH D PHGLGD LQGHSHQGH GD KHWHURJHQHLGDGH TXtPLFD GD
DPRVWUD
S2VPRPHWULD GH PHPEUDQD p LQGLFDGD SDUD SROtPHURV FRP ODUJD IDL[D GH SHVR
PROHFXODU $ OLPLWDomR SDUD SROtPHURV GH EDL[R SHVR PROHFXODU p GDGD SHOD
SHUPHDELOLGDGHGDPHPEUDQD
S2 PpWRGR IRUQHFH DLQGD LQIRUPDo}HV D UHVSHLWR GDV LQWHUDo}HV SROtPHUR
VROYHQWH
S2VP{PHWURVFRPHUFLDOL]DGRVDWXDOPHQWHSHUPLWHPPHGLUDSUHVVmRRVPyWLFDGH
XPDVROXomRVLPSOHVHPFHUFDGHDPLQ
$V GHVYDQWDJHQV GD RVPRPHWULD GH PHPEUDQD HVWmR SULQFLSDOPHQWH
UHODFLRQDGDVjVPHPEUDQDV
S6XSHUHVWLPDomRGRVYDORUHVGH M n VmRREVHUYDGRVTXDQGRRVROXWRSROtPHUR
VHGLIXQGHDWUDYpVGDPHPEUDQD&RQVHTHQWHPHQWHDPRVWUDVSROLGLVSHUVDVGH
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Tcnicas para
Determinao de Peso
Molecular Ponderal Mdio
5.1 Espalhamento de luz
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5.1.4 Espalhamento de luz em soluo de partculas pequenas
4XDQGR DV SDUWtFXODV HVSDOKDQWHV SRVVXHP WDPDQKR PHQRU GR TXH GR
FRPSULPHQWR GH RQGD GD OX] LQFLGHQWH D LQWHQVLGDGH GD OX] HVSDOKDGD , p D
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Razo de Rayleigh da soluo:
R , sol =
I , sol
Io
.r 2
(5.11)

Razo de Rayleigh do solvente puro:
R , o =
I , solvente
Io
.r 2
(5.12)
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(5.13)
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R , sol =
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(5.14)
I , benzeno
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(5.15)
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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

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=
intensidade da luz espalhada a um ngulo zero R0
(5.16)
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2

(5.18)
3DUDGHWHUPLQDURSHVRPROHFXODUHRUDLRGHJLUDomRGRQRYHORPDFURPROHFXODU
DUD]mR.F5pFRORFDGDHPJUiILFRYHUVXVRWHUPR>VHQNV@$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%(TXDomRHDSDUWLUGHVWHRUDLRGHJLUDomR
1 16 2 no2 2
B=
S
2
M
3o
(5.19)
$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

)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

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\OHLJK5 5VROXomR5VROYHQWH3RUWDQWRTXDOTXHU
FRQWDPLQDomRSRUSDUWtFXODVGHSRHLUDRXRXWUDVSDUWtFXODVWDQWRQDVROXomRRXQR
VROYHQWH SRGH DFDUUHWDU YDORUHV LQFRUUHWRV GH 5 &RQVHTHQWHPHQWH RV
SDUkPHWURV M w $ H UDLR GH JLUDomR QmR VHUmR UHSUHVHQWDWLYRV GD VROXomR HP

DQiOLVH e QHFHVViULR HQWmR HOLPLQDU DR Pi[LPR D TXDQWLGDGH GH SDUWtFXODV HVWUD
QKDVSRHLUDPLFURJpLVRXDJUHJDGRVFRQWLGDVWDQWRQRVROYHQWHTXDQWRQDVROXomR
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

$ 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]TXDVHHOiVWLFRTXDVLHODVWLFOLJKWVFDWWHULQJ
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

SRUWUDQVIRUPDGDGH)RXULHURHVSHFWURGHIUHTrQFLDVGHIOXWXDomR(VVHHVSHFWUR
pHQWmRDMXVWDGRSRUXPDFXUYDORUHQW]LDQD(TXDomRDSDUWLUGDTXDOREWpP
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'RpQHFHVViULRH[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
2UDLRKLGURGLQkPLFRGDVSDUWtFXODV5+pREWLGRGH'RXWLOL]DQGRD(TXDomRGH
6WRNHV(LQVWHLQ(TXDomR
RH =
kT
6Do
(5.24)
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

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
)LJXUDD)RUPD6GHXPDOLQKDHVSHFWUDOTXHpDODUJDGDSHORHIHLWR'RSSOHUHEIXQomRGRWHPSR

GHFRUUHODomR&WFRUUHVSRQGHQWHQRGRPtQLRGHWHPSR$ODUJXUDGDOLQKDpSURSRUFLRQDODRFRHILFLHQWH
GHGLIXVmRWUDQVODFLRQDO

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
HRWHPSRGHUHJLVWURpFXUWRGDRUGHPGHVRXPHQRU3RULVVRDLQWHQVLGDGH
GHHVSDOKDPHQWRH[LEHIOXWXDo}HVDFHQWXDGDVFRPRPRVWUDGRHVTXHPDWLFDPHQWHQD
)LJXUD
N
FDQDO
(A A ) = (A A )
0
i +1
RFDQDO
(A A ) = (A A )
i (0 )i (t ) = A A G (t )
QRFDQDO
i+n
(A A ) = (A A )
0
i+2
1

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

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)LJXUDRTXDOpDLQWHQVLGDGHGHHVSDOKDPHQWRTXHpUHJLVWUDGD
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

)LJXUD)XQomRGRWHPSRGHFRUUHODomRGDLQWHQVLGDGHGHHVSDOKDPHQWR*W LLW!GHXPD

VROXomRRUJkQLFDGHSROtPHURSROLGLVSHUVRFRPRXPDIXQomRGRWHPSRGHDWUDVR
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PROpFXODV GH FRPSRVLomR XQLIRUPH &RQVHTHQWHPHQWH FRPR R tQGLFH GH UHIUDomR
GHSHQGH GD FRPSRVLomR DV UHJUDV FOiVVLFDV VXVWHQWiYHLV HP XP VLVWHPD
SROLGLVSHUVR QmR VmR DSOLFiYHLV $OpP GLVVR HP FHUWRV FDVRV RV YiULRV WLSRV GH
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HVSDOKDPHQWR GH OX] HVWiWLFR FLWDP R XVR GH VROYHQWH LVRUUHIUDWLYRV 6ROYHQWH
LVRUUHIUDWLYRpDTXHOHTXHHPXPVLVWHPDGHGRLVFRPSRQHQWHV$H%SRVVXLtQGLFH
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GHWHFWDU R FRPSRQHQWH FRP tQGLFH GH UHIUDomR GLIHUHQWH GDTXHOH GR VROYHQWH
XWLOL]DGR $VVLP XWLOL]DQGR XP VROYHQWH LVRUUHIUDWLYR SDUD R FRPSRQHQWH $ p
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VH XP VROYHQWH LVRUUHIUDWLYR SDUD R FRPSRQHQWH % p SRVVtYHO GHWHUPLQDU R SHVR
PROHFXODUGDVHTrQFLD$1HVWHFDVRRVYDORUHVGHSHVRPROHFXODUVmRFDOFXODGRV
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YDULDGDVGHWHFWDQGRDLQWHQVLGDGHGHHVSDOKDPHQWRDkQJXORVWDPEpPYDULDGRVH
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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]HURYHU)LJXUD1RFDVRGHVLVWHPDVHPTXHKiD
IRUPDomR GH DJUHJDGRV QD IDL[D GH FRQFHQWUDomR DQDOLVDGD R JUiILFR GH =LPP
DSUHVHQWDVHFRPRFXUYDV)LJXUDeLPSRUWDQWHOHPEUDUHQWUHWDQWRTXHHP
FRQGLo}HV DGYHUVDV GH DQiOLVH SRHLUD OX] H[WHUQD HP H[FHVVR HWF R JUiILFR GH
=LPPWDPEpPVHDSUHVHQWDQDIRUPDGHFXUYDVPHVPRSDUDVROXo}HVGHPROpFXODV
QmRDJUHJDGDV
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$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[FOXVmRSRUWDPDQKRYHUFDStWXORLWHP
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[DGHSHVRVPROHFXODUHVGHD
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

(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

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
FRQFHQWUDomRFRPRXPDIXQomRGDSRVLomRUDGLDO2VVLVWHPDVySWLFRVPDLVFRPXQV
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

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
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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
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H[LVWHQWH
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VHGLPHQWDomR2VUHVXOWDGRVIRUQHFLGRVSHORPpWRGRGHYHORFLGDGHGHVHGLPHQWDomR
HP SULQFtSLR VmR PHQRV ULJRURVRV TXH DTXHOHV REWLGRV SRU HTXLOtEULR GH
VHGLPHQWDomR(QWUHWDQWRQDSUiWLFDSRUVHUGHPDLVIiFLOXWLOL]DomRRPpWRGRGH
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5.2.4 Velocidade de sedimentao
2 PpWRGR GH YHORFLGDGH GH VHGLPHQWDomR WHP VLGR XVDGR SDUD GRLV SURSyVLWRV
SULQFLSDLVFRPRXPFULWpULRGHSXUH]DGHPDWHULDLVELRTXtPLFRVHSDUDDPHGLGDGH

FRHILFLHQWHVGHVHGLPHQWDomR K sed (VWHFRHILFLHQWHVHUYHSDUDDFDUDFWHUL]DomRGH

PDWHULDLVHSDUDFiOFXORVGHSHVRPROHFXODUHSURSULHGDGHVKLGURGLQkPLFDV
$ FHQWUtIXJD p RSHUDGD D DOWDV YHORFLGDGHV SDUD WUDQVSRUWDU PROpFXODV GH
SROtPHURDWUDYpVGRVROYHQWHSDUDRIXQGRGDFpOXODVHDGHQVLGDGHGRVROYHQWHIRU
PHQRUTXHDGRSROtPHURRXSDUDRWRSRIORWDomRVHDGHQVLGDGHGRVROYHQWHIRU
PDLRU TXH D GR SROtPHUR $ WD[D GH PRYLPHQWR SRGH VHU PRQLWRUDGD SRU PHLR GD
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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 (TXDomRPDVDVPROpFXODVGHVORFDPXPDPDVVDGH
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
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F = m 2 r m 2 r 2 = m (1 2 )r 2 = ( M / N A )(1 2 )r 2 (5.29)
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(5.30)
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pDOFDQoDGDH
( M / N A )(1 2 )r 2 = 6RS (dr / dt )

(5.31)
$ YHORFLGDGH QR HVWDGR HVWDFLRQiULR HP XPD XQLGDGH GH FDPSR JUDYLWDFLRQDO
SRGHHQWmRVHUGHILQLGDFRPRDFRQVWDQWHGHVHGLPHQWDomR K sed
K sed = (1 / 2 r )(dr / dt )
(5.32)
$SDUWLUGD(TXDomRWHPVHTXH
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(5.33)
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D = kT / f
(5.34)
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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
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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


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]HURRSDWDPDUHDUHJLmRFHQWUtSHWDRQGHD
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
r =r
cr dr
c p ra
2
b
2
p
rp
r = r dc
2
b
ra
rp
dc
r = r
dr
dr
ra
2
b
(5.36)
rb
dc
(5.37)
ra
rp
dc
r dr dr
a
(5.38)
RQGH rp pRUDLRGHXPSRQWRQRSDWDPDU c p pDFRQFHQWUDomRQHVVHSRQWRHp ra

RUDLRGRPHQLVFR$VGLIHUHQWHVIRUPDVGHH[SUHVVmRSDUD rb VmRHTXLYDOHQWHVPDV
VmR~WHLVSDUDVLVWHPDVySWLFRVGLIHUHQWHV

)LJXUD3URFHVVRGHVHGLPHQWDomRHPXPDFpOXODGHXOWUDFHQWULIXJDomRVXEPHWLGDDURWDomRD
9DULDomRGDFRQFHQWUDomRDRORQJRGDFpOXODE*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
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K sed = kM a
(5.39)

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SROtPHUR GH M FRQKHFLGR SDUD XP GDGR SDU SROtPHURVROYHQWH D XPD GDGD
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IUDo}HV GR VROXWR GH GLIHUHQWHV SHVRV PROHFXODUHV HVWLYHUHP GLVSRQtYHLV HQWmR p
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IXQomRGH K sed
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Qual o efeito da concentrao sobre os resultados obtidos ?

2FRHILFLHQWHGHVHGLPHQWDomRGHFUHVFHFRPRDXPHQWRGDFRQFHQWUDomRGRVROXWR
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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
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FRP FHUWD IDFLOLGDGH $ YLVFRVLGDGH GD PDLRULD GDV VROXo}HV HVWXGDGDV HP XPD
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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

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
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PDFURPROHFXODU SROLGLVSHUVR UHGLVWULEXLVH GHQWUR GD FpOXOD $V PROpFXODV PDLV
SHVDGDV VHGLPHQWDPVH PDLV UiSLGR H QR HTXLOtEULR HODV DVVHQWDPVH PDLV
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8PD DQiOLVH GHWDOKDGD UHTXHU PHGLGDV GH GLYHUVDV VROXo}HV FRP FRQFHQWUDo}HV
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SHVRPROHFXODUTXDQWRRYDORUGRVHJXQGRFRHILFLHQWHGRYLULDO
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E p D XPD GLVWkQFLD r GR VHX FHQWUR GH URWDomR p GDGD SHOD (TXDomR H VHX
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(5.40)
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~ = ( M 2 2 r 2 / 2)
(5.41)
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~
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r r
(5.42)
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J = L M 2 r
r
(5.43)
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2 SRWHQFLDO TXtPLFR p XPD IXQomR GH T P H c 2 PDV VH T p FRQVWDQWH
HQWmR
P
= +
r P T ,C r c 2
HFRPR

= V2 = 2 M 2
P

c 2
c
2
T , P r
(5.44)
P
; = 2 r ;
r
RT
2
=
1 + c 2
c2
c 2
(5.45)
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2
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r
c
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(5.46)
6XEVWLWXLQGRD(TXDomRQD(TXDomRREWpPVH
RT c 2
J = L M 2 2 2 r M 2 2 r +
c 2 r
(5.47)
RX
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c
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(5.48)
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(5.49)
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1
c2
2
dc 2 rM 2 (1 2 )
=
dr
RT
(5.50)
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=
ln
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2 RT
(5.51)
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> c(m ) @HDGRIXQGRGDFpOXOD> c(b ) @
5HDUUDQMDQGRHLQWHJUDQGRD(TXDomRREWpPVH
M 2 (1 2 ) 2
dc
r dr dr =
RT
m
rb
rb
rc(r ) dr
(5.52)
rm
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c(b) c(m) =
2
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(5.53)
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2
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(5.54)
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SHVRPROHFXODUSRQGHUDOPpGLRDSDUWLUGHUHJLVWURVUHIUDWRPpWULFRVVHPXWLOL]DomR
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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

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6.2.1 Viscosidade real
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6.2.2 Viscosidade relativa
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6.2.3 Viscosidade intrnseca

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GR QRYHOR IRU FRQVLGHUDGR SURSRUFLRQDO j UDL] TXDGUDGD GR SHVR PROHFXODU GR
SROtPHURDYLVFRVLGDGHLQWUtQVHFDSRGHVHUH[SUHVVDFRPR
sp
[] = lim c
c 0
M
M
= M
(6.21)
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)
[] =
(6.23)
(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
3
K. . M 2
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
N M 1+ a
1
i i
a
M V = wi M ia = i =1
i =1
Ni M i
i =1
a
(6.24)
2VYDORUHVGH.HDGD(TXDomRSRGHPVHUGHWHUPLQDGRVH[SHULPHQWDOPHQWH
XWLOL]DQGRVHXPDVpULHKRPyORJDGHSROtPHURVPRQRGLVSHUVRVTXHGLIHUHPDSHQDV
QRSHVRPROHFXODU$VYLVFRVLGDGHVLQWUtQVHFDVGHVWHVSROtPHURVVmRGHWHUPLQDGDVH
UHODFLRQDGDV DR VHX UHVSHFWLYR SHVR PROHFXODU SRU PHLR GR ORJDULWPR GD (TXDomR

,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
WHWDVROYHQWHHWHPSHUDWXUDRIDWRUGHH[SDQVmRGRQRYHORGD(TXDomR
pLJXDODXPHDHTXDomRGDYLVFRVLGDGHSRGHVHUGHVFULWDFRPR
[] = K . M
(6.25)
VHQGRDFRQVWDQWH.GHILQLGDSHODVHJXLQWHHTXDomR
K =
r02

2
(6.26)
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

r02
2
(6.27)
$ (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

$)LJXUDUHSUHVHQWDXPQRYHORSROLPpULFRTXDQGRH[SDQGLGRHHQFROKLGR6H
RVROYHQWHLQWHUDJHSRXFRFRPDPDFURPROpFXODPDXVROYHQWHRFRQWDWRSROtPHUR
SROtPHURpPDLVSURYiYHOID]HQGRFRPTXHRQRYHORVHHQFROKD)LJXUDD6HR
VROYHQWH LQWHUDJH EHP FRP D PDFURPROpFXOD ERP VROYHQWH R FRQWDWR SROtPHUR
VROYHQWHpPDLVSURYiYHOGRTXHRFRQWDWRSROtPHURSROtPHURHRQRYHORVHH[SDQGH
)LJXUD E $ FDGHLD HQFROKLGD RIHUHFH PHQRV UHVLVWrQFLD KLGURGLQkPLFD
UHVLVWrQFLD DR IOX[RHSRUWDQWRVXDVROXomRDSUHVHQWDPHQRUYLVFRVLGDGHGRTXH
XPDVROXomRFRQWHQGRXPDFDGHLDHVWHQGLGDGHPHVPRSHVRPROHFXODU
)LJXUD(VTXHPDGDFRQIRUPDomRGHXPQRYHORSROLPpULFRHPIXQomRGDDILQLGDGHFRPRVROYHQWH
DHQFROKLGDEH[SDQGLGD
1R WySLFR DQWHULRU IRUDP GLVFXWLGDV DV GLPHQV}HV GH XPD PDFURPROpFXOD VRE
FRQGLo}HVWHWD1RFDVRHPTXHDPDFURPROpFXODpGLVVROYLGDHPXPERPVROYHQWH
DYLVFRVLGDGHLQWUtQVHFDpGHILQLGDFRPR
[] =
(6.28)
RQGH r p D GLVWkQFLD TXDGUiWLFD PpGLD GR QRYHOR HP XP VROYHQWH TXDOTXHU
GLIHUHQWHGRVROYHQWHWHWD(PXPVROYHQWHQmRLGHDORIDWRUGHH[SDQVmRGHYHVHU
FRQVLGHUDGRYHUFDStWXORRXVHMD
2

r02
(6.29)
9LVFRVLPHWULD
r02
&RQVLGHUDQGRD(TXDomRHDVVXPLQGRTXHDUD]mR
M pXPDIXQomRGD
HVWUXWXUD GD FDGHLD H LQGHSHQGH GR PHLR RX GR SHVR PROHFXODU D YLVFRVLGDGH
LQWUtQVHFDHPXPVROYHQWHTXDOTXHUSRGHVHUGHILQLGDFRPR
r02
=

2 1
M 2 3 = K .M 12 3
(6.30)
$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
>@pDYLVFRVLGDGHLQWUtQVHFDPHGLGDHPVROYHQWHWHWD
(6.31)

S(TXDomRGH6WRFNPD\HUH)L[PDQUHODFLRQDDYLVFRVLGDGHLQWUtQVHFDFRPXPD
TXDQWLGDGH%TXHpIXQomRGRSDUkPHWURGHLQWHUDomR.
[] = K.M + 0,51B.M
(6.32)
RQGH.pDFRQVWDQWHGHWHUPLQDGDHPFRQGLo}HVWHWD0pRSHVRPROHFXODUpD
FRQVWDQWH XQLYHUVDO GH )ORU\ H % p XPD TXDQWLGDGH UHODFLRQDGD DR SDUkPHWUR GH
LQWHUDomRSROtPHURVROYHQWHVHJXQGRD(TXDomR
B=
2
(1 2 )
v sp
(6.33)
V1 N A
RQGHYVSpRYROXPHHVSHFtILFRGRSROtPHUR9pRYROXPHPRODUGRVROYHQWHH1$pR
Q~PHURGH$YRJDGUR

6.7 Efeito do peso molecular na viscosidade

$ YLVFRVLGDGH GH VROXo}HV GLOXtGDV p EDVWDQWH DIHWDGD SHOR SHVR PROHFXODU 2
DXPHQWRGRSHVRPROHFXODUDXPHQWDDYLVFRVLGDGHLQWUtQVHFDHRFRHILFLHQWHDQJXODU
GD UD]mR VSF YHUVXV F SDUD XP PHVPR SDU SROtPHURVROYHQWH D XPD PHVPD
WHPSHUDWXUD$)LJXUDLOXVWUDRHIHLWRGRSHVRPROHFXODUQRSHUILOGD(TXDomRGH
+XJJLQVRQGH0!0!0
)LJXUD'HSHQGrQFLDGDYLVFRVLGDGHUHGX]LGDGHVROXo}HVGLOXtGDVFRPDFRQFHQWUDomRGHSROtPHURVGH
GLIHUHQWHVSHVRVPROHFXODUHV0!0!0!0
6.8 Viscosidade em solues de polieletrlitos

6ROXo}HVGHSROLHOHWUyOLWRVVmRPXLWRLQWHUHVVDQWHVSDUDVHHVWXGDURHIHLWRGDIRUPD
GDPDFURPROpFXODQDYLVFRVLGDGHGDVVROXo}HVGLOXtGDV$PROpFXODGHVWHVSROtPHURV
VRIUHYDULDo}HVFRQVLGHUiYHLVQRVHXYROXPHKLGURGLQkPLFRGHSHQGHQGRGRJUDXGH
GLVVRFLDomR7RPHPRVFRPRH[HPSORRSROLiFLGRDFUtOLFRRXSROLiFLGRPHWDFUtOL
FR (VWHV SROtPHURV DVVXPHP YROXPHV GLIHUHQWHV HP IXQomR GR S+ GR PHLR (P
VROXomR DTXRVD RV SROtPHURV HQFRQWUDPVH IUDFDPHQWH GLVVRFLDGRV H FRQWrP XP
SHTXHQRQ~PHURGHFDUJDVDRORQJRGDFDGHLD
4XDQGRXPDSHTXHQDTXDQWLGDGHGHKLGUy[LGRGHVyGLRRXSRWiVVLRpDGLFLRQDGD
D HVWDV VROXo}HV R SROLiFLGR UHDJH IRUPDQGR VDLV GH VyGLR RX SRWiVVLR (VWHV VDLV

9LVFRVLPHWULD
GLVVRFLDPVHPXLWREHPHPVROXo}HVDTXRVDVOLEHUDQGRRVFiWLRQVRTXHJHUDXP
JUDQGHQ~PHURGHFDUJDVQHJDWLYDVDRORQJRGDVFDGHLDVSROLPpULFDV(VWDVFDUJDV
VH UHSHOHP H D UHSXOVmR HOHWURVWiWLFD WHQGH D HVWLFDU DV FDGHLDV HQTXDQWR TXH D
PRELOLGDGHWpUPLFDWHQGHDHQFROKrODVPHGLGDTXHVHDXPHQWDRS+GRPHLRR
JUDXGHGLVVRFLDomRDXPHQWDHRQRYHORH[SDQGHVHFDGDYH]PDLVRFDVLRQDQGRXP
DXPHQWR VHQVtYHO QD YLVFRVLGDGH $ )LJXUD LOXVWUD HVWH HIHLWR RQGH REVHUYDVH
XPDFUpVFLPREUXVFRGDYLVFRVLGDGHUHGX]LGDDWpS+HPWRUQRGHUHJLmR%(VWH
DFUpVFLPR p DWULEXtGR QmR Vy DR DXPHQWR GR YROXPH PROHFXODU GHYLGR j UHSXOVmR
HOHWURVWiWLFDFRPRWDPEpPjVLQWHUDo}HVLQWHUPROHFXODUHVHQWUHRVkQLRQVGHXPD
FDGHLDHRVJUXSRViFLGRQmRGLVVRFLDGRVGHRXWUDFDGHLD2EYLDPHQWHHVWDVLQWHUD
o}HVVmRPDLRUHVFRPRDXPHQWRGDFRQFHQWUDomRGDVROXomRHSRUWDQWRRHIHLWRQD
YLVFRVLGDGHpDLQGDPDLRU
$ YLVFRVLGDGH GD VROXomR GH SROLiFLGR DXPHQWD FRP R DXPHQWR GR S+ DWp XP
OLPLWH)LJXUDSRQWR&$FLPDGHXPGHWHUPLQDGRYDORUGHS+DFRQFHQWUDomR
GHFRQWUDtRQVQDVROXomRFiWLRQVDXPHQWDPXLWRHHVWHVFRPHoDPDVHUDWUDtGRV
SHORVkQLRQVFDUER[LODWRSUHVHQWHVQDFDGHLDPDFURPROHFXODU2VFiWLRQVDVVRFLDGRV
DRV kQLRQV IRUPDP XPD HVSpFLH GH FREHUWXUD GD FDGHLD SROLPpULFD $V UHSXOV}HV
HOHWURVWiWLFDVHDVLQWHUDo}HVLQWHUPROHFXODUHVGHFUHVFHPUHVXOWDQGRHPXPHQFR
OKLPHQWR GR QRYHOR SROLPpULFR H FRQVHTHQWH GHFUpVFLPR GD YLVFRVLGDGH UHGX]LGD
GDVROXomRUHJLmR'
)LJXUD,QIOXrQFLDGRS+GRPHLRQDYLVFRVLGDGHUHGX]LGDGHVROXo}HVGHSROLHOHWUyOLWRVDYiULDV
FRQFHQWUDo}HV

6.9 Efeito da temperatura na viscosidade intrnseca

$ YLVFRVLGDGH LQWUtQVHFD SRGH DXPHQWDU RX GLPLQXLU FRP D WHPSHUDWXUD (VWH
IHQ{PHQRHVWiGLUHWDPHQWHUHODFLRQDGRFRPDDILQLGDGHWHUPRGLQkPLFDGHXPSDU
SROtPHURVROYHQWHRXVHMDFRPDGHSHQGrQFLDGRVHJXQGRFRHILFLHQWHYLULDOFRPD
WHPSHUDWXUD$)LJXUDLOXVWUDDGHSHQGrQFLDGH>@H$FRPDWHPSHUDWXUD6HD
DILQLGDGHWHUPRGLQkPLFDPHOKRUDFRPDWHPSHUDWXUD$DXPHQWDRQRYHORVRIUH
XP LQFKDPHQWR PDLRU SHOD DomR GR VROYHQWH H D YLVFRVLGDGH DXPHQWD FRPR
HVSHUDGR (VWH FRPSRUWDPHQWR p FDUDFWHUtVWLFR GH VLVWHPDV TXH DSUHVHQWDP
WHPSHUDWXUD FRQVROXWD VXSHULRU 8&67 YHU FDStWXOR 6H $ GHFUHVFH FRP R
DXPHQWRGDWHPSHUDWXUDRQRYHORFRQWUDLVHFDGDYH]PDLVHDYLVFRVLGDGHGLPLQXL
(VWH FRPSRUWDPHQWR p WtSLFR GH VLVWHPDV TXH SRVVXHP WHPSHUDWXUD FRQVROXWD
LQIHULRU/&67
)LJXUD9DULDomRGH>@H$HPIXQomRGDWHPSHUDWXUDSDUDVLVWHPDVTXHDSUHVHQWDPFRPSRUWDPHQWRGR
WLSRD8&67HE/&67
6.10 Tamanho molecular de polmeros ramificados

$YLVFRVLGDGHLQWUtQVHFDGHXPSROtPHURHPVROXomRpXPSDUkPHWURTXHGHSHQGH
GLUHWDPHQWHGDVGLPHQV}HVPROHFXODUHVFRPRGLVFXWLGRDQWHULRUPHQWH2WDPDQKR
PROHFXODU GH XP SROtPHUR GLVVROYLGR HP XP GHWHUPLQDGR VROYHQWH SRGH VHU
HVWLPDGRDSDUWLUGDYLVFRVLGDGHLQWUtQVHFDHGHSHQGHGHXPDVpULHGHIDWRUHVWDLV
FRPR
SSHVRPROHFXODU

9LVFRVLPHWULD
SHVWUXWXUDORFDOGDFDGHLDGHILQLGDSHORIDWRU
r02
SHIHLWRGRVROYHQWHHVWLPDGRSHORIDWRUGHH[SDQVmR
SHVWUXWXUD GD FDGHLD FRPR XP WRGR HP TXH R JUDX GH UDPLILFDomR p XP IDWRU
LPSRUWDQWH
3DUD SROtPHURV OLQHDUHV D GLVWkQFLD H[WUHPRDH[WUHPR TXDGUiWLFD PpGLD

p XPD PHGLGD PXLWR XVDGD SDUD GHILQLU DV GLPHQV}HV PROHFXODUHV

3ROtPHURV UDPLILFDGRV HQWUHWDQWR SRVVXHP YiULDV H[WUHPLGDGHV GH FDGHLD H HVWH
SDUkPHWUR QmR SRGH VHU XWLOL]DGR 3DUD HVWHV FDVRV XWLOL]DVH R UDLR GH JLUDomR
r2
TXDGUiWLFRPpGLR s 2
2YROXPHRFXSDGRSRUXPSROtPHURUDPLILFDGRpVHPSUHPHQRUGRTXHRYROXPH
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GLPHQV}HV HQWUH XP SROtPHUR OLQHDU H XP SROtPHUR UDPLILFDGR GH PHVPR SHVR
PROHFXODU XWLOL]DVH R SDUkPHWUR g (VWH SDUkPHWUR p GHWHUPLQDGR D SDUWLU GH
PHGLGDV GR UDLR GH JLUDomR GD PDFURPROpFXOD OLQHDU H UDPLILFDGD HP FRQGLo}HV
WHWD RX VHMD FRQGLo}HV QmRSHUWXUEDGDV SRU LQWHUDo}HV SROtPHURSROtPHUR RX
SROtPHURVROYHQWH2SDUkPHWUR g pGHWHUPLQDGRDSDUWLUGD(TXDomR
s02
ramif
g=
s2
0 lin
(6.34)
&RPR RV SROtPHURV UDPLILFDGRV SRVVXHP GLPHQV}HV PHQRUHV GR TXH SROtPHURV
OLQHDUHV D SHVR PROHFXODU FRQVWDQWH R YDORU g VHUi VHPSUH PHQRU GR TXH D
XQLGDGH
2 HIHLWR GD UDPLILFDomR SRGH WDPEpP VHU HVWXGDGR D SDUWLU GH PHGLGDV GH
YLVFRVLGDGHLQWUtQVHFD1HVWHFDVRXWLOL]DVHRSDUkPHWUR g RQGHDUD]mRHQWUHDV
YLVFRVLGDGHVpFRQVLGHUDGD
[] , ramif
g =
[] , lin
(6.35)
4XDQGR D VROXomR SROLPpULFD p HVWXGDGD HP ERQV VROYHQWHV R FRHILFLHQWH GH

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VH H[SDQGLU PXLWR PDLV GR TXH XP SROtPHUR UDPLILFDGR ,VWR VLJQLILFD TXH R
SDUkPHWUR g RX g HVWLPDGR HP ERP VROYHQWH GHYHUi VHU PXLWR PHQRU GR TXH
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QXPHULFDPHQWHPHQRU3ROtPHUROLQHDU3ROtPHURUDPLILFDGR(VWDGRWHWD
2HIHLWRGRVROYHQWHQRSDUkPHWUR g RX g pEHPH[HPSOLILFDGRXWLOL]DQGRVH
SROtPHURV GR WLSR HVWUHOD $ )LJXUD LOXVWUD R FRPSRUWDPHQWR GH SROtPHURV
UDPLILFDGRV HP FRQGLo}HV WHWD H HP SUHVHQoD GH XP ERP VROYHQWH 8P SROtPHUR
OLQHDU FRQVHJXH VH H[SDQGLU PXLWR PDLV GR TXH XP SROtPHUR UDPLILFDGR SRUTXH
QHVWH ~OWLPR DV OLJDo}HV FRYDOHQWHV HQWUH DV FDGHLDV OLPLWDP R VHX FRHILFLHQWH GH
H[SDQVmR
&RQVLGHUHPRVDJRUDRVSROtPHURVUDPLILFDGRVGRWLSRHVWUHODFRPRLOXVWUDGRQD
)LJXUD RV TXDLV SRVVXHP UDPLILFDo}HV GH PHVPR SHVR PROHFXODU $VVLP
DXPHQWDQGRRQ~PHURGHUDPLILFDo}HVDXPHQWDRSHVRPROHFXODU3RUpPRYROXPH
KLGURGLQkPLFRQmRVRIUHPXGDQoDVFRQVLGHUiYHLV&RQVHTHQWHPHQWHDYLVFRVLGDGH
GHVWHVSROtPHURVSHUPDQHFHSUDWLFDPHQWHFRQVWDQWH
)LJXUD([SDQVmRGRQRYHORPROHFXODUGHXPSROtPHUROLQHDUHXPSROtPHURUDPLILFDGRHPERPVROYHQWH

9LVFRVLPHWULD
)LJXUD5HSUHVHQWDomRHVTXHPiWLFDGHSROtPHURVUDPLILFDGRVGRWLSRHVWUHODFRPUDPLILFDo}HVGH
PHVPRSHVRPROHFXODUHFRPQ~PHURGHUDPLILFDo}HVGLIHUHQWH

(VWDVGLIHUHQoDVGHFRPSRUWDPHQWROHYDUDPDOJXQVSHVTXLVDGRUHVDGHVHQYROYHU
PRGHORVTXHUHODFLRQDPRSDUkPHWUR g FRPRQ~PHURGHUDPLILFDo}HVIGHXP
SROtPHUR HVWUHOD 2V PRGHORV PDLV FLWDGRV QD OLWHUDWXUD VmR RV GH 6WRFNPD\HU H
)L[PDQHRGH=LPPH.LOEHDVUHVSHFWLYDVHTXDo}HVHVWmRDSUHVHQWDGDVDVHJXLU
Modelo de Stockmayer e Fixman
g = f
2 2
f +2
2 ( f 1)
(6.36)
RQGHIpRQ~PHURGHUDPLILFDo}HVGHXPSROtPHURHVWUHOD
Modelo de Zimm e Kilb
3 [0,39( f 1)+ 0,196]

2
2
f
g =
(6.37)
0,586
6.11 Tcnicas experimentais

5HVXOWDGRV SUHFLVRV GH PHGLGDV GH YLVFRVLGDGH HP VROXomR VmR SRVVtYHLV VRPHQWH
TXDQGRVHFRQKHFHDFRQFHQWUDomRH[DWDGDVROXomRHTXDQGRHVWDVVROXo}HVHVWmR
OLYUHV GH TXDOTXHU SDUWtFXOD HP VXVSHQVmR FRPR SRU H[HPSOR SRHLUD PDWHULDO
LQVRO~YHOHWF$OpPGLVVRpLPSRUWDQWHTXHHVWDVVROXo}HVQmRVHMDPPXLWRGLOXtGDV

QHP PXLWR FRQFHQWUDGDV 6ROXo}HV PXLWR GLOXtGDV DSUHVHQWDP D YLVFRVLGDGH PXLWR

SUy[LPD GD YLVFRVLGDGH GR VROYHQWH SXUR GLILFXOWDQGR D PHGLGD 3RU RXWUR ODGR
VROXo}HV PXLWR FRQFHQWUDGDV QmR REHGHFHP D PDLRULD GDV UHODo}HV GLVFXWLGDV
DQWHULRUPHQWHGHYLGRDLQWHUDo}HVHQWUHPROpFXODVGRSUySULRSROtPHURFRHILFLHQWH
GH DWULWR GD VROXomR FRP D SDUHGH GR FDSLODU HWF $OJXQV RXWURV FXLGDGRV WDPEpP
GHYHPVHUWRPDGRVWDLVFRPR
S'HYHPVHUHYLWDGRVVROYHQWHVFRPDOWDYRODWLOLGDGHQDWHPSHUDWXUDGHWUDEDOKR
XPDYH]TXHDVXDHYDSRUDomRSURPRYHDYDULDomRGDFRQFHQWUDomRGDVROXomR
S$ FRQFHQWUDomR LQLFLDO LGHDO SDUD PHGLGDV GH YLVFRVLGDGH p DTXHOD TXH IRUQHFH
YLVFRVLGDGHUHODWLYDHPWRUQRGH$OJXQVDXWRUHVVXJHUHPDUD]mRGH
S$ VROXomR PDLV GLOXtGD GHYH DSUHVHQWDU XPD YLVFRVLGDGH UHODWLYD GH QR PtQLPR

S7UDEDOKDQGRVH QD IDL[D GH YLVFRVLGDGH UHODWLYD HQWUH H DV HTXDo}HV GH
+XJJLQV H .UDHPHU VmR DSOLFiYHLV H RV GDGRV SRGHP VHU WUDWDGRV GH PDQHLUD
OLQHDU
S$ VROXomR GHYH VHU SUHYLDPHQWH ILOWUDGD XWLOL]DQGRVH ILOWURV DGDSWDGRV
GLUHWDPHQWHDXPDVHULQJD
S2 FRQWUROH GD WHPSHUDWXUD p GH H[WUHPD LPSRUWkQFLD SDUD D YLVFRVLPHWULD HP
VROXomR$YDULDomRGHWHPSHUDWXUDGHYHVHUGDRUGHPGHR&
'LYHUVRV WLSRV GH YLVFRVtPHWUR HVWmR GLVSRQtYHLV QR PHUFDGR $ )LJXUD
DSUHVHQWDGRLVWLSRVGHYLVFRVtPHWURRYLVFRVtPHWURFRQKHFLGRFRPR8EEHORKGHD
HRGH&DQQRQ)HQVNHE1RSULPHLURFDVRDGLOXLomRGDVROXomRPmHpIHLWDGHQWUR
GRYLVFRVtPHWUR(VWHYLVFRVtPHWURUHTXHUXPYROXPHLQLFLDOGHP/SDUDDVROXomR
PmHHDGLOXLomRpUHDOL]DGDDGLFLRQDQGRVHDOtTXRWDVGHVROYHQWH
2 YLVFRVtPHWUR GR WLSR &DQQRQ)HQVNH QmR SHUPLWH GLOXLomR GHQWUR GR YLVFR
VtPHWURSRUTXHRYROXPHGDVROXomRGHYHVHUFRQVWDQWH
6XEVWkQFLDVTXHVHGLVVROYHPVRPHQWHDWHPSHUDWXUDVDOWDVFRPRpRFDVRGDV
SROLROHILQDVQHFHVVLWDPGHYLVFRVtPHWURHVSHFLDOFRPRRLOXVWUDGRQD)LJXUD$V
PHGLGDVVmRUHDOL]DGDVHPDWPRVIHUDLQHUWHQLWURJrQLRSDUDHYLWDUGHJUDGDomRGR
SROtPHUR GXUDQWH R H[SHULPHQWR 2 YLVFRVtPHWUR DSUHVHQWDGR QD )LJXUD
SHUPLWHTXHDILOWUDomRGDDPRVWUDHDVPHGLGDVGHYLVFRVLGDGHVHMDPUHDOL]DGDVHP
DWPRVIHUD LQHUWH 2 SROtPHUR H R VROYHQWH VmR LQWURGX]LGRV DWUDYpV GR WXER 2
YLVFRVtPHWURpHQWmRHYDFXDGRHSUHHQFKLGRFRPQLWURJrQLRYiULDVYH]HVDWUDYpV
GDWRUQHLUD2VLVWHPDpHQWmRDTXHFLGRjWHPSHUDWXUDGHVHMDGDSDUDGLVVROXomR
GRSROtPHUR$SyVDGLVVROXomRGRSROtPHURDTXHQWHDVROXomRpHPSXUUDGDDWUDYpV
GR ILOWUR GH YLGUR VLQWHUL]DGR XWLOL]DQGRVH SUHVVmR GH QLWURJrQLR (VWH SURFHVVR p
IHLWR DEULQGRVH D WRUQHLUD DR PHVPR WHPSR HP TXH VH PDQWpP D WRUQHLUD
IHFKDGD3DUDIDFLOLWDUDILOWUDomRDWUDYpVGRILOWURDWRUQHLUDpLQWHUPLWHQWHPHQWH

9LVFRVLPHWULD
DEHUWD 2 WHPSR GH IOX[R p PHGLGR FRP DV WRUQHLUDV H DEHUWDV SDUD D
DWPRVIHUDGHQLWURJrQLR
)LJXUD7LSRVGHYLVFRVtPHWURD8EEHORKGHHE&DQQRQ)HQVNH
)LJXUD9LVFRVtPHWURXVDGRSDUDPHGLGDVDWHPSHUDWXUDVHOHYDGDV

2VYLVFRVtPHWURVFDSLODUHVGHYHPVHUVHOHFLRQDGRVGHPRGRTXHDSUHVHQWHPXP
GLkPHWURGHFDSLODUWDOTXHRWHPSRGHHVFRDPHQWRGRIOXLGRRFRUUDQDIDL[DHQWUH
HVHJXQGRV
$ VHJXLU p DSUHVHQWDGR R SURFHGLPHQWR SDUD D UHDOL]DomR GDV PHGLGDV GH
YLVFRVLGDGH
3UHSDUDU D VROXomRPmH FRP FRQFHQWUDomR DGHTXDGD 1RUPDOPHQWH GLVVROYHVH
FHUFD GH J GH SROtPHUR HP P/ GH VROYHQWH XWLOL]DQGRVH EDOmR
YROXPpWULFR
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SURPRYHU FRPSOHWD VROXELOL]DomR $ VROXomR GHYH HVWDU OtPSLGD 6H WLYHU DOJXP
PDWHULDOHPVXVSHQVmRGHYHVHDTXHFHUOHYHPHQWHDVROXomR
)LOWUDUDVROXomRPmHHPILOWURDSURSULDGRSDUDHOLPLQDUTXDOTXHUSDUWtFXODHP
VXVSHQVmR
0HGLU D FRQFHQWUDomR H[DWD GD VROXomRPmH UHWLUDQGRVH XPD DOtTXRWD FRP
SLSHWD YROXPpWULFD WUDQVIHULQGRD SDUD XPD FiSVXOD GH DOXPtQLR GH SHVR
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VROYHQWHWHQWUHRVGRLVPHQLVFRVGRFDSLODUGLIHUHQoDVHQWUHRVSRQWRV$H%
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5HPRYHURVROYHQWHHVHFDULQWHUQDPHQWHRYLVFRVtPHWURGHPRGRHILFLHQWH
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Cromatografia
7.1 Introduo
7pFQLFDV FURPDWRJUiILFDV FRQVWLWXHP SURFHVVRV GH VHSDUDomR GH VXEVWkQFLDV
RUJkQLFDV (P XP SURFHVVR FURPDWRJUiILFR DV VXEVWkQFLDV D VHUHP VHSDUDGDV VmR
FDUUHDGDV SRU XPD IDVH TXH VH PRYH IDVH PyYHO DR ORQJR GH XPD RXWUD IDVH
HVWDFLRQiULD OHLWR FURPDWRJUiILFR $V IDVHV PyYHO H HVWDFLRQiULD FRQVWLWXHP GXDV
IDVHVLPLVFtYHLV$DPRVWUDFRQWHQGRDVVXEVWkQFLDVpFRORFDGDQDIDVHPyYHOHHVVDV
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

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
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S &URPDWRJUDILDSRUDGVRUomRDIDVHHVWDFLRQiULDSRVVXLFHQWURVDWLYRVFDSD]HVGH
DGVRUYHUHP RV FRPSRQHQWHV GD PLVWXUD D VHU DQDOLVDGD $ DGVRUomR p
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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

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7.2.1 Eficincia da coluna

$ HILFLrQFLD GD FROXQD p PHGLGD HP WHUPRV GH Q~PHUR GH SUDWRV WHyULFRV 1 GH
DFRUGRFRPD(TXDomR
t
N = 16 R
w
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N = 5,5 R
w1
2
(7.1)
RQGH1pRQ~PHURGHSUDWRVWHyULFRVW5pRWHPSRGHUHWHQomRUHODWLYRDRPi[LPR
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GHWHUPLQDomRGRQ~PHURGHSUDWRVWHyULFRV

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$ (TXDomR FRPSDUD D ODUJXUD GR SLFR FRP R WHPSR HP TXH R FRPSRQHQWH
ILFRXUHWLGRQDFROXQD2Q~PHURGHSUDWRVWHyULFRVpSURSRUFLRQDODRFRPSULPHQWR
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HILFLrQFLD GD FROXQD GH XPD IRUPD LQGHSHQGHQWH GR Q~PHUR GH SUDWRV WHyULFRV
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HETP =
L
N
(7.2)
RQGH/pRFRPSULPHQWRGDFROXQDJHUDOPHQWHHPPLOtPHWURVH1pRQ~PHURGH
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GH+(736HFRPSDUDUPRVFROXQDVGHPHVPRFRPSULPHQWR/DHILFLrQFLDVHUiWDQWR
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$ 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
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YHORFLGDGHGRIOX[RXWLOL]DGRQRVH[SHULPHQWRVQmRSRGHVHUPXLWREDL[DQHPPXLWR
DOWD $ FXUYD DSUHVHQWDGD QD ILJXUD p R UHVXOWDGR GD FRPSRVLomR GH YiULRV IDWRUHV
TXHLQIOXHQFLDPDDOWXUDGRSUDWRWDLVFRPRSURFHVVRGHGLIXVmRLUUHJXODULGDGHGH
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HIHLWRGDGLIXVmRPROHFXODUEHIHLWRGDUHVLVWrQFLDjWUDQVIHUrQFLDGHPDVVD
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
=
t R1 t m
K1
(7.3)
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

S FRHILFLHQWHGHGLVWULEXLomRQDFURPDWRJUDILDGHWURFDL{QLFD
2YROXPHGHUHWHQomRGHXPSLFRHPXPDFURPDWRJUDILDOtTXLGDpGHILQLGRFRPR
V R = Vm + KVest
(7.4)
RQGH
9P YROXPHGDIDVHPyYHOQRVLQWHUVWtFLRVGRUHFKHLRGDFROXQDRXVHMDRYROXPH
PRUWR
9HVW YROXPHGDIDVHHVWDFLRQiULDQDFURPDWRJUDILDGHSDUWLomRRX
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7.2.3 Resoluo
2 REMHWLYR GD FURPDWRJUDILD p VHSDUDU RV FRPSRQHQWHV GH XPD PLVWXUD HP XP
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DSDUWLUGD(TXDomR
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EDQGDVEFURPDWRJUDPDFRPUHVROXomRPHOKRUDGDGHYLGRDRDXPHQWRGDHILFLrQFLDGDFR OXQDF
FURPDWRJUDPDFRPUHVROXomRPHOKRUDGDGHYLGRDRDXPHQWRGDVHOHWLYLGDGH
7.3 Cromatografia gasosa

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

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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
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GHYDSRUpPHQRUUHVXOWDQGRHPXPWHPSRPDLRUGHUHWHQomRGRVROXWRQDFROXQD
7.3.1.2 Descrio do cromatgrafo

$ )LJXUD DSUHVHQWD R HVTXHPD GH XP FURPDWyJUDIR JDVRVR FXMDV SDUWHV
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UHFRPHQGDVH KLGURJrQLR KpOLR RX DUJ{QLR FRPR JiV FDUUHDGRU SRUTXH HVWHV
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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
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&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
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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
XPDFROXQDFRQVWLWXtGDSRUXPyOHRPLQHUDOGHQDWXUH]DDSRODUFRPRIDVHOtTXLGD
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
FRQVWLWXtGDGHSROLJOLFROHWLOrQLFR&$5%2:$;3ROLJOLFROHWLOrQLFRXWLOL]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

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
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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
$V SULQFLSDLV DSOLFDo}HV GD FURPDWRJUDILD JDVRVD QD iUHD GH SROtPHURV HVWmR
GHVFULWDVDVHJXLU
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$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
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QHFHVViULRXPSLUROLVDGRUDFRSODGRDRFURPDWyJUDIRDJiV$DOWDWHPSHUDWXUDGR
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SDUD VHUHP FDUUHDGRV SHOD IDVH PyYHO (VWDV SHTXHQDV PROpFXODV RULJLQDGDV GD
GHFRPSRVLomRGRSROtPHURSDVVDPSHODFROXQDFURPDWRJUiILFD2FURPDWRJUDPD

&URPDWRJUDILD
REWLGRDSDUWLUGHVWDWpFQLFDpGHQRPLQDGRSLURJUDPDHVXDIRUPDGHSHQGHGDV
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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
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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
HVSHFtILFR9JFRUULJLGRD&FRPRH[SUHVVRQD(TXDomR
Vg =
273,2 VR 273,2
K
=
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(7.6)
RQGH 95 p R YROXPH GH UHWHQomR j WHPSHUDWXUD DEVROXWD 7 Z p D PDVVD GD IDVH
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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
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ln V g
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RQGH+pDHQWDOSLDGDVROXomRH5pDFRQVWDQWHXQLYHUVDOGRVJDVHV

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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
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FULVWDOLQD7P
SHVWXGRVWHUPRGLQkPLFRVGHVROXo}HVSROLPpULFDV
SGHWHUPLQDomRGDFULVWDOLQLGDGHGHXPDIDVHHVWDFLRQiULDSROLPpULFD
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IDVH SROLPpULFD p LPSHGLGD $ UHWHQomR RFRUUH SULQFLSDOPHQWH GHYLGR jV
DGVRUo}HV VXSHUILFLDLV H R GLDJUDPD GH UHWHQomR p OLQHDU QHVWD UHJLmR 1HVWH
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GHQWUR GD PDVVD SROLPpULFD ,VWR ID] FRP TXH R YROXPH GH UHWHQomR HVSHFtILFR
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6HJPHQWR %& QHVWD UHJLmR GH WHPSHUDWXUD R FRHILFLHQWH GH GLIXVmR GR VROXWR
GHQWURGDPDVVDSROLPpULFDDXPHQWDFRPRDXPHQWRGDWHPSHUDWXUD
3RQWR&QHVWHSRQWRRSURFHVVRGHGLIXVmRDWLQJHRHTXLOtEULR
6HJPHQWR&'QHVWDUHJLmRGHWHPSHUDWXUDTXHHVWiDEDL[RGDWHPSHUDWXUDGH
IXVmRGRSROtPHURDUHWHQomRRFRUUHGHYLGRjVRUomRGRVROXWRGHQWURGDPDVVD
SROLPpULFD$VLQWHUDo}HVSROtPHURVROXWRVmRUHVWULWDVDRVGRPtQLRVDPRUIRVGD
IDVHSROLPpULFDHVWDFLRQiULD
6HJPHQWR')QHVWDUHJLmRGHWHPSHUDWXUDH[DWDPHQWHDEDL[RGDWHPSHUDWXUD
GHIXVmRDIUDomRGDIDVHDPRUIDDXPHQWDRFDVLRQDQGRXPDXPHQWRQRYROXPH
GHUHWHQomR
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6HJPHQWR)*QHVWDUHJLmRDFLPDGD7PRFRUUHDVRUomRGRVROXWRGHQWURGDIDVH
SROLPpULFD FRPSOHWDPHQWH DPRUID H R GLDJUDPD GH UHWHQomR p OLQHDU
([WUDSRODQGRVH HVWD OLQKD D EDL[DV WHPSHUDWXUDV D SRUomR FULVWDOLQD GD IDVH
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SDeterminao da temperatura de transio vtrea
$GHWHUPLQDomRGDWHPSHUDWXUDGHWUDQVLomRYtWUHD7JGRSROtPHURTXHFRQVWLWXLD
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SDeterminao da cristalinidade de um polmero
$ GHWHUPLQDomR GD FULVWDOLQLGDGH GH SROtPHURV QD IDVH HVWDFLRQiULD p EDVHDGD QD
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Xa =
Vg
V g
(7.8)
RQGH9JpRYDORUGRYROXPHGHUHWHQomRUHDOPHGLGRH9
JpRYDORUGRYROXPHGH
UHWHQomRTXHVHULDH[LELGRVHDDPRVWUDIRVVHFRPSOHWDPHQWHDPRUID2EYLDPHQWH
DPERVGHYHPVHUPHGLGRVDXPDPHVPDWHPSHUDWXUD
2 JUDX GH FULVWDOLQLGDGH ;F GD IDVH HVWDFLRQiULD REWLGR HP SRUFHQWDJHP SRGH
VHUFDOFXODGRGHDFRUGRFRPD(TXDomR
X c = 1001 g
V g
(7.9)
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IRUQHFLGRSHOD(TXDomR

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X c , max = 1001 g (equil )

V g

(7.10)
RQGH 9JHTXLO p R YROXPH GH UHWHQomR GR SROtPHUR QR SRQWR GH HTXLOtEULR HQWUH DV
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SDeterminao do coeficiente de difuso de um polmero
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SLFR2FRHILFLHQWHGHGLIXVmRGHXPVROXWRQDIDVHSROLPpULFDHVWDFLRQiULDSRGHVHU
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DODUJDPHQWRGRSLFRpXPDIXQomRGDVSURSULHGDGHVGDFROXQDHSRGHVHUH[SUHVVR
HPWHUPRVGDDOWXUDHTXLYDOHQWHDRSUDWRWHyULFR+(73
HETP = A + B v + Cv
(7.11)
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TXHOHYDHPFRQVLGHUDomRRDODUJDPHQWRGDEDQGDGHYLGRDRSUySULRLQVWUXPHQWR
%pDGLIXVmRPROHFXODUH&pXPDFRQVWDQWHUHODFLRQDGDDRWHPSRILQLWRQHFHVViULR
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8d 2
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(7.12)
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K=
(t R t M )
tM
(7.13)
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2 YDORU GH +(73 SRGH VHU GHWHUPLQDGR D SDUWLU GD ODUJXUD GRV SLFRV GR VROXWR
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SRGHVHUFDOFXODGR
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([LVWH DLQGD RXWUR WLSR GH FROXQD HP TXH R SROtPHUR p GHSRVLWDGR VREUH
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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
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OtTXLGROtTXLGRRQGHDDPRVWUDpGLVWULEXtGDHQWUHGRLVOtTXLGRVLPLVFtYHLVTXH
FRQVWLWXHPDIDVHPyYHOHDIDVHHVWDFLRQiULD
&URPDWRJUDILD GH DGVRUomR (VWD WpFQLFD FURPDWRJUiILFD p FRQVLGHUDGD GR WLSR
OtTXLGRVyOLGRRQGHDIDVHPyYHOpXPOtTXLGRHDIDVHHVWDFLRQiULDpXPVyOLGR
&URPDWRJUDILDGHWURFDL{QLFD(VWDWpFQLFDGHSHQGHGDFDSDFLGDGHGHDGVRUomR
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L{QLFRFRPDOWDSRURVLGDGHFRPRIDVHHVWDFLRQiULD
$FURPDWRJUDILDOtTXLGDGRWLSROtTXLGRVyOLGRSRGHVHUGHGHVHQYROYLPHQWRRX
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XPDFDPDGDILQDGHXPVyOLGRFRPRIDVHHVWDFLRQiULDHVSDOKDGDHPXPDVXSHUItFLH
SODQDSRUH[HPSOROkPLQDGHYLGUR
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VHQGR D IDVH PyYHO HOXtGD DWUDYpV GD FROXQD $ FURPDWRJUDILD GH HOXLomR SRGH VHU
UHDOL]DGDUHFKHDQGRVHXPDFROXQDGHYLGURFRPXPVXSRUWHDSURSULDGRVtOLFDRX
DOXPLQDVHQGRDIDVHPyYHOHOXtGDOHQWDPHQWHDWUDYpVGHVWDFROXQD
3DUDH[SHULPHQWRVHPODERUDWyULRXWLOL]DVHDWpFQLFDGHVHSDUDomRSRUDGVRUomR
WDQWR SDUD D FURPDWRJUDILD GH FDPDGD ILQD 7/& FRPR SDUD D FURPDWRJUDILD GH
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$QiOLVHV PDLV HODERUDGDV HQYROYHQGR D FURPDWRJUDILD OtTXLGD UHTXHUHP
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7.4.1 Descrio do cromatgrafo lquido de alta eficincia

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FURPDWRJUDILD OtTXLGD GH DOWD UHVROXomR +3/& SDUWLomR DGVRUomR H H[FOXVmR SRU
WDPDQKR$VGLIHUHQoDVHQWUHHVWHVPpWRGRVVmRJRYHUQDGDVSHODQDWXUH]DGDIDVH
HVWDFLRQiULDFRPRYHUHPRVPDLVWDUGH$)LJXUDDSUHVHQWDXPGLDJUDPDGHXP
FURPDWyJUDIROtTXLGR
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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

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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
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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
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SHUPDQHFH QR UHVHUYDWyULR SHTXHQR ORRS HQTXDQWR TXH R VROYHQWH p
FRQVWDQWHPHQWHERPEHDGRSDUDDVFROXQDVVHPDUUDVWDUDDPRVWUDDVHUDQDOLVDGD
6HRYROXPHGDVROXomRLQMHWDGDIRUPDLRUGRTXHDFDSDFLGDGHGRORRSRUHVWRGD
VROXomRpHOLPLQDGRFRPRUHMHLWR
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TXHDFRQGX]LUiDWpDVFROXQDV

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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
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VROYHQWHV PXLWR SRODUHV QmR SRGHP VHU XWLOL]DGRV TXDQGR D IDVH HVWDFLRQiULD p
KLGURIyELFD

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S2EVHUYDU RV OLPLWHV GH SUHVVmR SDUD TXH DV SDUWtFXODV PDQWHQKDP D VXD
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FURPDWRJUDILD GH DGVRUomR SRUpP GHYH VHU HYLWDGD HP FURPDWRJUDILD GH
H[FOXVmRSRUWDPDQKR
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PDQWLGDDXPDWHPSHUDWXUDHQWUHH&DILPGHGLPLQXLUDYLVFRVLGDGHGD
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7.4.1.5 Detectores
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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
$)LJXUDDSUHVHQWDXPHVTXHPDGDOX]UHIUDWDGDQHVWHWLSRGHFpOXOD2kQJXOR
UHSUHVHQWDRkQJXORGHGHIOH[mRTXHRIHL[HGHOX]VRIUHDSyVDWUDYHVVDURVGRLV
FRPSDUWLPHQWRV 4XDQGR RV GRLV FRPSDUWLPHQWRV VmR RFXSDGRV SHOR VROYHQWH
)LJXUDDREVHUYDVHXPkQJXORGHGHIOH[mRFRUUHVSRQGHQWHD$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

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]DDVROXomRHFpDFRQFHQWUDomRGDVHVSpFLHVTXH
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
)LJXUD6LQDOREWLGRGHXPGHWHFWRUGHXOWUDYLROHWDGRWLSRDGLRGHDUUD\HEFRPSULPHQWRGHRQGD

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[FOXVmRSRUWDPDQKRYHUFDStWXOR

.p.r 4
=
8.L.Q
(7.16)
RQGH SpDGLIHUHQoDGHSUHVVmRDRORQJRGRFDSLODUGRYLVFRVtPHWURUpRUDLRGR
FDSLODU/pRFRPSULPHQWRGRFDSLODUH4pDYHORFLGDGHGHIOX[RGROtTXLGRPHGLGD
HPYROXPHSRUXQLGDGHGHWHPSR
$YLVFRVLGDGHGDVROXomRHOXHQWHGRFURPDWyJUDIRGHH[FOXVmRSRUWDPDQKRSRGH
VHUGHWHUPLQDGDGHGXDVIRUPDV
SPHGLGDGRWHPSRQHFHVViULRSDUDXPGHWHUPLQDGRYROXPHGHHOXHQWHDWUDYHVVDU
RFDSLODUGRYLVFRVtPHWUR
SPHGLGDGDTXHGDGHSUHVVmRUHVXOWDQWHGDSDVVDJHPGRHOXHQWHQRFDSLODU
(PERUDRSULPHLURPpWRGRVHMDSRVVtYHOSDUDPHGLGDVGHYLVFRVLGDGHRIIOLQH
TXDQGRRYLVFRVtPHWURpDFRSODGRDXPVLVWHPDFURPDWRJUiILFRPHGLGDVRQOLQH
D GHWHUPLQDomR GD TXHGD GH SUHVVmR IRUQHFH XPD PHGLGD FRQWtQXD GD YLVFRVLGDGH
GDVROXomR
1RV YLVFRVtPHWURV RQOLQH XWLOL]DGRV HP FURPDWRJUDILD OtTXLGD D TXHGD GH
SUHVVmR GD DPRVWUD HOXHQWH SL p PHGLGD QR FDSLODU H FRPSDUDGD j TXHGD GH
SUHVVmRSURYRFDGDSHORVROYHQWHSXUR S$WpFQLFDpEDVHDGDQDGHWHUPLQDomRGD
YLVFRVLGDGHLQWUtQVHFDLQVWDQWkQHD>@LXWLOL]DQGRD(TXDomR
[ ]i =
1
p 1 p p0
1
log i log i = i
ci
0 ci
p0 ci p0
(7.17)
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
QRUPDOPHQWHRGHWHFWRUGHtQGLFHGHUHIUDomRYHUFDStWXOR
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
1
Kc
=
+ 2 A2 c + 3 A3 c 2 + ......
R M
(7.19)
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
PHGLGDVGHSHVRPROHFXODUFURPDWRJUDILDGHH[FOXVmRSRUWDPDQKRDVVXPHVHTXH
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

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$WpFQLFDGHSHQGHGDVLQWHUDo}HVHVSHFtILFDVGRVROXWRFRPDVXSHUItFLHGH
XPDGVRUYHQWHIDVHHVWDFLRQiULDILQDPHQWHGLYLGLGR
&RQVLGHUHPRV XP FDVR EHP VLPSOHV XPD VXEVWkQFLD RX DPRVWUD 6 HP XP
HOXHQWH ( &RQVLGHUHPRV DLQGD TXH D DGVRUomR H GHVVRUomR VmR SURFHVVRV
UHYHUVtYHLV$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
n
(
S ads )(Em )
K=
(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{PHURSDUDGHQRPLQDGRKLGURTXLQRQDpFDSD]GH
LQWHUDJLUFRPGRLVFHQWURVDWLYRVVLPXOWDQHDPHQWH2LV{PHURRUWRGHQRPLQDGR
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

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
R
DSUHVHQWDGRVQD7DEHODFRVWXPDVHXWLOL]DUPLVWXUDVGHVROYHQWHV

7DEHOD6pULHHOXRWUySLFDSDUDDOXPLQD
6ROYHQWH
QSHQWDQR
LVRFWDQR
FLFORKH[DQR
WHWUDFORUHWRGHFDUERQR
[LOHQR
WROXHQR
EHQ]HQR
pWHUHWtOLFR
FORURIyUPLR
WHWUDKLGURIXUDQR
DFHWRQD
DFHWRQLWULOD
LSURSDQRO
PHWDQRO
R

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
FURPDWRJUDILDOtTXLGROtTXLGRHFURPDWRJUDILDSRUIDVHOLJDGDERXQGHGSKDVH
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[

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
K =
Cs
Cm
(7.22)
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 '=
gs
(7.23)
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'
Cm g m Vs
Vs
(7.26)
RX

&URPDWRJUDILD
Vs
K '= K
Vm
(7.27)
$ 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
HQYROYHPXPDUHDomRFRPRJUXSRUHDWLYRVLODQRO6L2+QDVXSHUItFLHGDVtOLFD
2 SULPHLUR PpWRGR HQYROYH D UHDomR GH HWHULILFDomR HQWUH RV JUXSRV VLODQRO GR
VXSRUWHHRVJUXSRVKLGUR[LODVLWXDGRVQDH[WUHPLGDGHGHXPDFDGHLDGHXPiOFRRO
$V OLJDo}HV pWHU VmR IDFLOPHQWH KLGUROLViYHLV H VmR WDPEpP WHUPLFDPHQWH
LQVWiYHLV 3RUWDQWR HVWH WLSR GH IDVH HVWDFLRQiULD QmR p DGHTXDGR SDUD PXLWDV
DSOLFDo}HV
Si
OH
HOR
Si
OR
)DVHV TXLPLFDPHQWH OLJDGDV HQYROYHQGR UHDo}HV GH VLODQL]DomR WrP VH WRUQDGR
PDLV SRSXODUHV SRUTXH D OLJDomR VLOR[DQD 6L26L p PDLV HVWiYHO HP VROYHQWHV
FRPXQVGHFURPDWRJUDILD$OLJDomR6L&OTXHQmRUHDJLXSRGHVHUKLGUROLVDGDD6L2+
HHPVHJXLGDUHDJLGDFRP&+6L&O
(VWH WLSR GH HPSDFRWDPHQWR p JHUDOPHQWH HVWiYHO HP S+ QD IDL[D GH D H
WHPSHUDWXUDVDWp&
Si
OH
R2SiCl2
R
Si
O-SiCl + HCl
R
8P WHUFHLUR WLSR GH UHDomR HQYROYH D XWLOL]DomR GH FORUHWR GH WLRQLOD 2 FORUR
OLJDGRDRiWRPRGHVLOtFLRpHQWmRVXEVWLWXtGRSRUXPJUXSR5DOTXLODTXDOTXHUD

SDUWLUGHXPDUHDomRGHVXEVWLWXLomRQXFOHRItOLFDHQYROYHQGRUHDJHQWHGH*ULJQDUG
RXXPDDPLQDVXEVWLWXtGD
RMgBr
Si
Si
NHR
SOCl2
Si
OH
Si
Cl
RNH2
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 SROLFORUHWR 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
JOLFRO
(VWUXWXUD
OH OH
(CH2)3-O-CH2-CH-CH2
Si
DPLQR
Si
(CH2)3 NH2
QLWUR
Si
(CH2)3 NO
2
R[DQLWULOD
(CH2)3-OCH2CH2 CN
Si
QLWULOD
(CH2)3 CN
Si
DPLQRDULOD
NH2
QLWURDULOD
NO2
GLPHWLODPLQD
DOLOIHQLOD
(CH2)3 N(CH3)2
Si
Si
IHQLOD
CH2 CH=CH2
Si
QKH[LOD
Si
(CH 2)5CH 3
QRFWLOD
Si
(CH2)7CH3
QRFWDGHFLOD
Si
(CH 2)17CH 3

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[FOXVmRSRUWDPDQKR6(&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(&

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
FRUUHVSRQGHDRYROXPHLQWHUVWLFLDOPDLVRYROXPHGHSRURV9R9SHSRULVVRHODV
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
LQWHUVWLFLDO9R
2YROXPHGHHOXLomR9HGHXPVROXWRpGDGRSHODVHJXLQWHHTXDomR
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/GHVROYHQWHGHQWURGRVSRURVYROXPH
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

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
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9.8 Exemplos de curvas de TG tpicas e aplicaes no estudo de

polmeros
9.8.1 Estabilidade trmica de polmeros
$
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$
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da razo metacrilato de metil/azobisisobutironitrila (MMA/AIBN) na
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(DTA) e Calorimetria
Diferencial de Varredura
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10.1 Introduo
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10.3 Calorimetria diferencial de varredura (DSC)

10.3.1 Comparao com o DTA
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10.3.2 Aplicaes gerais do DSC

'HVWHPRGRHQWUHDVDSOLFDo}HVGR'6&SRGHPVHUFLWDGDV
determinao das temperaturas de transio em polmeros

SWUDQVLomRYtWUHD7J
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SWHPSHUDWXUDGHIXVmR7P
medidas quantitativas
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10.3.3 Procedimento experimental
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Procedimento operacional:
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10.3.4 Anlise da curva de DSC
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WUDQVLo}HV&RPRH[HPSORYDPRVFLWDUDOHLWXUDGH7JH7P
10.3.4.1 Determinao da temperatura de fuso (Tm)

$7PSRGHVHUWRPDGDHPSRQWRVFRPRPRVWUDD)LJXUDDQRLQtFLRGRSLFR
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SLFR VmR GHWHUPLQDGDV QD LQWHUVHomR GRV SURORQJDPHQWRV 2 SRQWR D GHQRWD D
IXVmRGRVSULPHLURVFULVWDLVRSRQWREDIXVmRGDPDLRULDGRVFULVWDLVHRSRQWRF
DWHPSHUDWXUDHPTXHRFRUUHDIXVmRGHWRGRVRVFULVWDLV
)LJXUD'HWHUPLQDomRGDWHPSHUDWXUDGHIXVmRFULVWDOLQD7PGHXPDFXUYDGH'6&QRLQtFLRGDIXVmR
7QRPi[LPRGRSLFR7QRILPGDIXVmR7
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
GHYHVHUOLGDQRSRQWRD$OHLWXUDQRSRQWRESRGHVHUXVDGDSDUDHVWDEHOHFHUD
WHPSHUDWXUD QD TXDO D PDLRULD GRV FULVWDLV VH IXQGHP $ OHLWXUD QR SRQWR F p
DGRWDGDTXDQGRIRUGHLQWHUHVVHHVWDEHOHFHUDWHPSHUDWXUDFRUUHVSRQGHQWHjIXVmR
FRPSOHWDGRVFULVWDLV

10.3.4.2 Determinao da temperatura de transio vtrea (Tg)

2YDORUGH7JWDPEpPSRGHVHUGHWHUPLQDGRSRUPpWRGRVGLVWLQWRVFRPRPRVWUDD
)LJXUDDQRLQtFLRGDWUDQVLomR7EQDPHLDDOWXUDGRVSURORQJDPHQWRV7
HFQRSRQWRGHLQIOH[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&

6HDPHGLGDTXHHVWiVHQGRIHLWDpGH7JpPDLVDFRQVHOKiYHOXVDURPpWRGRE
SRUTXHSHUPLWHPHGLURXWURVSDUkPHWURVFRPRDODUJXUDGDWUDQVLomRYtWUHD7JH
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
QDWHPSHUDWXUDPDLVDOWD2UHJLVWURGHVHMDGRFRUUHVSRQGHjOLQKDDGD)LJXUD

SUHSHWLU R SURFHGLPHQWR SDUD XPD PDVVD FRQKHFLGD GH XPD VXEVWkQFLD SDGUmR
FRPRSRUH[HPSORDVDILUDy[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

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

$ 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

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

)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

'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

7DEHOD7UDQVLo}HVUHODFLRQDGDVDRVSURFHVVRVItVLFRVHTXtPLFRVTXHRFRUUHPGXUDQWHRDTXHFLPHQWR
7UDQVLomR
(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

;
3URFHVVR
$ )LJXUD DSUHVHQWD DV LQIRUPDo}HV WtSLFDV IRUQHFLGDV SHOR '6& SDUD
DPRVWUDVGHSROtPHURV

)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 SROLPHWDFULODWR 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

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$HFRSROtPHURVJUDIWL]DGRVGH300$FRPSROLy[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

SRVLFLRQDGRV QR PHLR GD FDGHLD H WDPEpP PHQRU R Q~PHUR GH HPDUDQKDPHQWRV
IRUPDGRVSHODVFDGHLDVRVTXDLVGLILFXOWDPRPRYLPHQWRPROHFXODU
)LJXUD9DULDomRGD7JHPIXQomRGRSHVRPROHFXODU
8PDH[FHomRDHVWHFRPSRUWDPHQWRRFRUUHSDUDRSROLy[LGRGHHWLOHQR3(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
)LJXUD9DULDomRGD7JHPIXQomRGRSHVRPROHFXODUGHDPRVWUDVGHSROLy[LGRGHHWLOHQR

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)LJXUDDRPLVWXUDUHVVHVGRLVSROtPHURVQDSURSRUomR
HVWHV SRGHP IRUPDU XPD PLVWXUD LPLVFtYHO SDUFLDOPHQWH PLVFtYHO RX

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

$7JGDPLVWXUDPLVFtYHOYDLGHSHQGHUGDFRPSRVLomRGHVVDPLVWXUDFRPRLOXVWUD
D)LJXUD8PPDLRUWHRUGRSROtPHUR$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

1
Tg AB
W A WB
+
Tg A Tg B
(10.4)
RXHQWmRSRUPHLRGDHTXDomRGH*RUGRQ7D\ORU
Tg =
W ATgA + WBTgB
W A + kWB
(10.5)
RQGHNpXPSDUkPHWURGHILQLGRSHODUD]mRGDYDULDomRGRFRHILFLHQWHGHH[SDQVmR
WpUPLFDLHQWUHRHVWDGRERUUDFKRVRHRHVWDGRYtWUHRGRVKRPRSROtPHURV$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

7DEHOD5HODo}HVSDUDSUHYHUDGHSHQGrQFLDGD7JFRPDFRPSRVLomRHPVLVWHPDVPLVWRVPLVFtYHLV
$XWRU
5HJUDGDV
PLVWXUDV
)R[
*RUGRQ
7D\ORU
(TXDomR
Tg AB = W A .Tg A + WB .Tg B
1
Tg AB
Tg =
W A WB
+
Tg A Tg B
WATgA + WBTgB
WA + kWB
W T + kW TgB
A gA
B
&RXFKPDQ
Tg =
WA + kWB
VHPHOKDQWHD
GH*RUGRQ
sendo k = Cp B
7D\ORU
Cp A
W A Cp A ln Tg A + W B Cp B ln Tg B
&RXFKPDQ
ln Tg AB =
&RXFKPDQ
Tg AB =
%HDWW\H
3RFKDQ
ln Tg AB = W A . ln Tg A + WB . ln Tg B
W A Cp A + W B Cp B
W A Cp ATg A + W B Cp B Tg B
W A Cp A + W B Cp B
2EVHUYDomR
6H7J$7J%DVIXQo}HVORJ
GD(TSRGHPVHU
H[SDQGLGDV
(10.3)
(10.4) 6H&SL7JLIRUFRQVWDQWH

HVWD(TLJXDODVHj(T
(10.5) K = B / A
(10.6)
$GHTXDGDSLQWHUDo}HV
HVSHFtILFDVPXLWRIUDFDVRX
DXVHQWHVTgA/TgB 1
(10.7) (TXDomRWHyULFDTXHGiRULJHP
jVGHPDLV
(10.8) 6H7J$7J%D(TSRGH
VHUVLPSOLILFDGD
(10.9) 6H&S$ &S%HVWD(T
LJXDODVHj(T
$UD]mR
Cp B pXVDGD
K=
8WUDFNL
&RXFKPDQH
.DUDV]
8WUDFNLH
&RXFKPDQ
ln Tg AB =
Tg AB =
WA . ln TgA + kWB . ln TgB
QD(T
WA + kWB
A A .Tg A + B B Tg B
ln Tg AB =
(10.10)
(10.11)
9PJ9PO
(10.12)
3DUDVLVWHPDVPXOWLFRPSRQHQWHV
A A + B B
Wn Cp n . ln Tg n
Wn Cp n
Cp A
$H%VmRDVGLIHUHQoDVQRFRHILFLHQWHGHH[SDQVmRWpUPLFDQRHVWDGRYtWUHRHQRHVWDGRERUUDFKRVRSDUD
XPFRPSRQHQWHQpRQ~PHURGHFRPSRQHQWHV

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$RILQDOGDDQiOLVH7IDDPRVWUDHQFRQWUDVHIXQGLGD
GHQWURGDFiSVXOD$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[D7LDDPRVWUDHQFRQWUDVHQRHVWDGRVyOLGRWHQGRDGTXLULGR
QRYDPHQWH PRUIRORJLD VHPLFULVWDOLQD $VVLP DR SURFHGHU QRYR DTXHFLPHQWR D
R&PLQDWp7IVHUiREVHUYDGDXPDFXUYDFRPRDGD)LJXUDD1HVWHSRQWRD
DPRVWUD HQFRQWUDVH QRYDPHQWH IXQGLGD QD FiSVXOD 6H DJRUD VXEPHWHUPRV HVWD
DPRVWUDDXPUHVIULDPHQWRUiSLGRTXHQFKLQJDWp7LWHPSHUDWXUDDEDL[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)LJXUDF0DLVXPDYH]DDPRVWUDHQFRQWUD
VHQDFiSVXODQRHVWDGRIXQGLGRSURQWDSDUDTXDOTXHUWLSRGHWUDWDPHQWRWpUPLFR
GHVHMDGR

)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

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
x(t )

kt n
= 1 e
(10.13)
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
dH
0 dt dt
x (t ) =
dH
0 dt dt
t
(10.14)
WRPDQGRW FRPRRLQVWDQWHHPTXHVHDWLQJHRHTXLOtEULRWpUPLFRHW FRPR

RILQDOGRSURFHVVRGHFULVWDOL]DomRHRQGHG+GWpDWD[DGHIOX[RGHFDORUH[WpD
IUDomRHPPDVVDGHPDWHULDOFULVWDOL]DGRQRWHPSRW
&RQVLGHUDQGR TXH DV LQWHJUDLV UHSUHVHQWDP iUHDV D HTXDomR DFLPD SRGH VHU
HVFULWDQDIRUPD
x(t ) =
At
A
(10.15)
RQGH$WpDiUHDVREDFXUYDGHFULVWDOL]DomRGHVGHRLQVWDQWH]HURDWpRLQVWDQWHWH
$pDiUHDWRWDOVREDFXUYDGHFULVWDOL]DomR
$JUDQGH]D[WUHODFLRQDRJUDXGHFULVWDOLQLGDGHGHVHQYROYLGRHPFDGDLQVWDQWH
FRP D FULVWDOLQLGDGH WRWDO DVVRFLDGD D GHWHUPLQDGDV FRQGLo}HV H[SHULPHQWDLV
3RUWDQWRRYDORUQRUPDOL]DGRGH[WYDULDGH]HURD
$SDUWLUGRSLFRH[RWpUPLFRREWpPVHRVYDORUHVGH[WHPIXQomRGHW
Como utilizar esses valores para chegar em k e n ?

$(TXDomRGH$YUDPLSRGHVHUPDWHPDWLFDPHQWHUHDUUDQMDGDGRVHJXLQWHPRGR
x(t ) = 1 e ( kt
n)
1 x(t ) = e ( kt
n)
ln1 ln x(t ) = kt n
(10.16)

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
FUHVFLPHQWR

(VIHUXOLWR
'LVFR
%DVWmR
1XFOHDomR
,QVWDQWkQHD

(VSRUiGLFD

+HWHURJrQHD
!Q!
!Q!
!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
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)LJXUD,VRWHUPDVGHFULVWDOL]DomRGHPDWHULDOSROLPpULFR3(7
10.3.8.7 Determinao de porcentagem de cristalinidade

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

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]DGRPDLVUHJL}HVFULVWDOLQDVRXPDLRUJUDXGHFULVWDOLQLGDGHHQWmR
XPDPDLRUTXDQWLGDGHGHFDORUVHUiDEVRUYLGDQDIXVmR2RSRVWRpREVHUYDGRSDUD
DPRVWUDVFRPSHTXHQDSRUFHQWDJHPGHUHJL}HVFULVWDOLQDV/RJRDSRUFHQWDJHPGH
FULVWDOLQLGDGHpFDOFXODGDGLUHWDPHQWHSRU
% de cristalinidade =
H f A
H f A 100% cristalino
x 100
(10.17)
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

10.3.8.8 Identificao de componentes de misturas de polmeros semicristalinos

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
TXtPLFD GDV PHVPDV 3RUpP D LQWHUSHQHWUDomR GH FDGHLDV GH SROtPHURV GLVWLQWRV
QDV UHJL}HV FULVWDOLQDV GHSHQGH QmR Vy GD DILQLGDGH TXtPLFD FRPR WDPEpP GH
GLYHUVRV IDWRUHV WDPEpP Mi PHQFLRQDGRV WDLV FRPR UHJXODULGDGH H VLPHWULD HQWUH
DV FDGHLDV $VVLP VH Mi QmR p PXLWR FRPXP HQFRQWUDU GRLV KRPRSROtPHURV FRP
UHJL}HV DPRUIDV FRP FRPSOHWD LQWHUSHQHWUDomR GH VXDV FDGHLDV FRPSOHWD
PLVFLELOLGDGHpIiFLOSHUFHEHUDGLILFXOGDGHGHHQFRQWUDUGRLVKRPRSROtPHURVFRP
LQWHUSHQHWUDomRGHFDGHLDVQDVUHJL}HVFULVWDOLQDV,VWRVXJHUHTXHDRPLVWXUDUGRLV
RX PDLV KRPRSROtPHURV VHPLFULVWDOLQRV DV VXDV UHJL}HV FULVWDOLQDV WHQGHP D VH
PDQWHU SUDWLFDPHQWH LQDOWHUDGDV H SRU FRQVHJXLQWH VXDV 7PV WDPEpP (VWH
FRPSRUWDPHQWR SHUPLWH HQWmR TXH PLVWXUDV GH FRPSRQHQWHV SRVVDP VHU
LGHQWLILFDGDVDWUDYpVGDWHPSHUDWXUDGHIXVmRGHVXDVUHJL}HVFULVWDOLQDV
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
FDORUHVGHIXVmRLVWRpHQWUHDViUHDVVRERVSLFRVGHIXVmRGDVUHJL}HVFULVWDOLQDV
GRVUHVSHFWLYRVSROtPHURVQDPLVWXUD
&RPR GLVFXWLGR QR LWHP DQWHULRU PLVWXUDV GH GRLV KRPRSROtPHURV VHPLFULV
WDOLQRV DSUHVHQWDUmR GRLV SLFRV UHODWLYRV jV 7PV GDV UHJL}HV FULVWDOLQDV GRV UHVSHF
WLYRV KRPRSROtPHURV PDQWLGDV SUDWLFDPHQWH LQDOWHUDGDV $VVLP D DQiOLVH GH XPD
PLVWXUDV GH GRLV KRPRSROtPHURV VHPLFULVWDOLQRV D R&PLQ QR LQWHUYDOR GH WHP
SHUDWXUD RQGH RFRUUHP DV GXDV 7PV DSUHVHQWD XPD FXUYD FRPR PRVWUD D )LJXUD


)LJXUD3LFRVGHIXVmRREVHUYDGRVHPXPDPLVWXUDGHSROtPHURVVHPLFULVWDOLQRV
$UHODomRHQWUHRVFDORUHVGHIXVmRSRGHVHUH[SUHVVDHPWHUPRVGDSRUFHQWDJHP
GD iUHD GR SLFR UHODWLYR j IXVmR GR FRPSRQHQWH HP PHQRU TXDQWLGDGH 3$ 1HVWH
FDVR
PA =
rea DEF
x 100
rea ABC + rea DEF
(10.18)
$SRUFHQWDJHPGHiUHDHQFRQWUDGDQmROHYDGLUHWDPHQWHDRWHRUGRFRPSRQHQWH
HP PHQRU TXDQWLGDGH QD PLVWXUD SRUTXH VDEHPRV TXH D IXVmR GH FDGD DUUDQMR
FULVWDOLQR HQYROYH XPD DEVRUomR GH FDORU FDUDFWHUtVWLFD $VVLP ID]VH QHFHVViULR
UHDOL]DU XPD FDOLEUDomR FRP PLVWXUDV GH FRPSRVLo}HV FRQKHFLGDV SDUD R SDU GH
SROtPHURV HP TXHVWmR &RPR SURFHGLPHQWR VmR SUHSDUDGDV DOJXPDV PLVWXUDV GH
FRPSRVLo}HV FRQKHFLGDV H FDGD XPD GHVVDV PLVWXUDV p DQDOLVDGD QR '6& SDUD
GHWHUPLQDomR GH VXDV SRUFHQWDJHQV GH iUHD GR SLFR UHODWLYR j IXVmR GD UHJLmR
FULVWDOLQD GR FRPSRQHQWH HP PHQRU TXDQWLGDGH &RP HVVHV GDGRV p SRVVtYHO
FRQVWUXLU XPD FXUYD GH FDOLEUDomR GH WHRU GH XP FRPSRQHQWH QD PLVWXUD YHUVXV
SRUFHQWDJHPGDiUHDGRSLFRUHODWLYRjIXVmRGRFRPSRQHQWHHPPHQRUTXDQWLGDGH
e LPSRUWDQWH REVHUYDU TXH FRPR D iUHD GR SLFR YDULD FRP R JUDX GH
FULVWDOLQLGDGHDFXUYDGHFDOLEUDomRGHYHVHUREWLGDDSDUWLUGHDPRVWUDVFRPJUDXV
GHFULVWDOLQLGDGHFRQVWDQWHVHDDPRVWUDGHVFRQKHFLGDWDPEpPGHYHVHUFRQVWLWXtGD

GH SROtPHURV FRP JUDXV GH FULVWDOLQLGDGH LJXDLV DRV GDV DPRVWUDV XVDGDV SDUD D
REWHQomRGDFXUYDSDGUmR,VWRSRGHVHUFRQWURODGRSHODKLVWyULDWpUPLFDGDPLVWXUD
'XDV RXWUDV WpFQLFDV GHVHQYROYLGDV D SDUWLU GD FDORULPHWULD GLIHUHQFLDO GH
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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&PRGXODGR0'6&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
WHPSHUDWXUDPpGLDGDDPRVWUDYDULDFRQWLQXDPHQWHFRPRWHPSRHPXPPRGRQmR
OLQHDU $ )LJXUD PRVWUD XP SHUILO GH DTXHFLPHQWR WtSLFR GR 0'6& $
FDSDFLGDGHGHFRPELQDUWD[DVGHDTXHFLPHQWRDOWDVLQVWDQWkQHDVFRPXPDWD[DGH
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YDQWDJHPWHyULFDGR'6&PRGXODGRpTXHHVWHUHVROYHDUHVSRVWDGRIOX[RGHFDORU
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Qual a importncia da medida ser resolvida em duas componentes?

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10.5 Fotocalorimetria diferencial

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YiULRV LQLFLDGRUHV TXtPLFRV VREUH D YHORFLGDGH GH FXUD GH VLVWHPDV SROLPpULFRV 2
SULPHLURHTXLSDPHQWRIRLPRQWDGRDGDSWDQGRVHXPDIRQWHGHOX]XOWUDYLROHWDDXP
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FRPHUFLDO DFRSODGR D XP FRPSXWDGRU FRP SURJUDPD DGHTXDGR DR WLSR GH DQiOLVH
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FXUD LQGX]LGD SRU UDGLDomR 89 FRPR XPD IXQomR GD FRQFHQWUDomR GH XP GDGR
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11.1 Deformaes mecnicas em materiais
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(11.1)
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(11.2)
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11.2 Anlise termomecnica (TMA)

11.2.1 Introduo
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WHPSHUDWXUD GHWHFWDGD WDPEpP GHYH YLU DFRPSDQKDGR GR PRGR GH RSHUDomR
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11.2.2 Calibrao do instrumento

$QWHV GH LQLFLDU D DQiOLVH R HTXLSDPHQWR GHYH VHU FDOLEUDGR 7RGD D FDOLEUDomR GR
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11.2.3 Modo de expanso
2V HQVDLRV GH H[SDQVmR VmR HIHWXDGRV GH PRGR D IRUQHFHU RV FRHILFLHQWHV GH
H[SDQVmRWpUPLFDOLQHDUDQWHVHGHSRLVGDRFRUUrQFLDGDWUDQVLomRGRHVWDGRYtWUHR
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2V FRUSRV GH SURYD GHYHP DSUHVHQWDU iUHD VXSHUILFLDO HP WRUQR GH PP H
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WUDQVLomRYtWUHD

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IXVmR
$ WHPSHUDWXUD GH WUDQVLomR YtWUHD p REWLGD SHOR PpWRGR FRQKHFLGR FRPR

WHPSHUDWXUDLQLFLDORQVHWTXHGHWHUPLQDDWHPSHUDWXUDDSUR[LPDGDRQGHRFRUUH
R LQtFLR GD WUDQVLomR (VWH SRQWR p REWLGR SHOD LQWHUVHomR GRV SURORQJDPHQWRV GH
GXDVUHWDV3RURXWURODGRFDGDVHJPHQWRGDFXUYDDSUHVHQWDGDQRVJUiILFRVUHODWD
XPDYDULDomRTXHGHVFUHYHRFRHILFLHQWHGHH[SDQVmRWpUPLFD$RVHUGHWHUPLQDGR
XP LQWHUYDOR GH WHPSHUDWXUD SRGHUi VHU REWLGR R FRHILFLHQWH GH H[SDQVmR OLQHDU
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(11.3)
RQGH pRFRHILFLHQWHGHH[SDQVmR /pDYDULDomRGDDOWXUDGDDPRVWUD 7pD

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$WHPSHUDWXUDGHIXVmRpREWLGDQRSRQWRRQGHRFRUUHXPDYDULDomREUXVFDQDV
GLPHQV}HVGDDPRVWUDTXDQGRVRESURJUDPDGHDTXHFLPHQWR

11.2.4 Modo de compresso

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
YDULDomR GH WHPSHUDWXUD (VWH PRGR GH HQVDLR SHUPLWH D REWHQomR GR PyGXOR GH
<RXQJSRUPHLRGHFiOFXORVTXHVHUmRDSUHVHQWDGRVQRVH[HPSORVGHDSOLFDomR
$ FDOLEUDomR GHVWH PRGR RSHUDFLRQDO p UHDOL]DGD GH PRGR DQiORJR DR GH
H[SDQVmR
2VFRUSRVGHSURYDVmRSUHSDUDGRVGHPRGRVHPHOKDQWHDRXWLOL]DGRSDUDPRGR
GH H[SDQVmR )LOPHV FRP GLPHQV}HV DSUR[LPDGDV GH PP [ PP [ PP H
VXSHUItFLHV D PDLV SODQD SRVVtYHO VmR FRORFDGRV QR WXER GD DPRVWUD $ VRQGD GH
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HIHWXDQGRVHHQWmRDPHGLGDGDDOWXUDGRFRUSRGHSURYD$WHPSHUDWXUDGRIRUQR
SRGH VHU UHGX]LGD DWp R SRQWR GHVHMDGR VHQGR XWLOL]DGR XP EDQKR GH JHOR VHFR H
iOFRRO FDVR VHMD QHFHVViULR $SyV D HVWDELOL]DomR GD WHPSHUDWXUD p GDGR LQtFLR DR
HQVDLR FRP FLFORV GH DTXHFLPHQWR H UHVIULDPHQWR FRQWtQXRV PDQWHQGRVH D FDUJD
FRQVWDQWH 2 UHVXOWDGR DSDUHFH VRE D IRUPD GH JUiILFR GH FRPSUHVVmR DOWXUD HP
SRUFHQWDJHPYHUVXVWHPSHUDWXUDPRVWUDGRQD)LJXUD
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QRPpWRGRHPSUHJDGRQRVHQVDLRVGHH[SDQVmR
11.2.5 Modo de penetrao
2 PRGR RSHUDFLRQDO GH SHQHWUDomR SHUPLWH D LGHQWLILFDomR GR SRQWR GH
DPROHFLPHQWRGRPDWHULDODQDOLVDGR
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WHPSHUDWXUDVGHDPROHFLPHQWRGHSDGU}HVFRPRRtQGLRHRHVWDQKR$FDOLEUDomR
GHVWHPRGRRSHUDFLRQDOpUHDOL]DGDGHPRGRDQiORJRDRGHH[SDQVmR

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GHSHQGHQGRGDVWUDQVLo}HVDSUHVHQWDGDVSHODDPRVWUDVmRREVHUYDGDVXPDRXPDLV
GHIOH[}HV QR JUiILFR GH SHQHWUDomR YHUVXV WHPSHUDWXUD $ )LJXUD PRVWUD R
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GD OHLWXUD LQLFLDO 2 PpWRGR PDLV LQGLFDGR VHULD D GHWHUPLQDomR GR SRQWR GH
LQIOH[mRFRQWXGRQHPVHPSUHpSRVVtYHOLGHQWLILFiORGHPRGRFODURPHVPRFRPR
DX[tOLRGDFXUYDREWLGDSHODSULPHLUDGHULYDGDGDFXUYDUHJLVWUDGD

)LJXUD&XUYDGH70$QRPRGRSHQHWUDomRGHXPPDWHULDOSROLPpULFRTXHDSUHVHQWDRVSURFHVVRVGH
WUDQVLomRYtWUHDFULVWDOL]DomRHIXVmR
11.2.6 Modo de flexo

(VWH HQVDLR VHJXH R SULQFtSLR GHVFULWR SHOR PpWRGR $670 ' RQGH VmR
GHWHUPLQDGDVDVWHPSHUDWXUDVHPTXHDGHIOH[mRDWLQJHXPYDORUHVSHFtILFR
7DPEpP QHVWH FDVR D FDOLEUDomR p IHLWD GH PRGR VHPHOKDQWH DR PRGR GH
H[SDQVmRQHFHVVLWDQGRVRPHQWHGHXPDFRUUHomRFDVRRHTXLSDPHQWRMiWHQKDVLGR
FDOLEUDGRHPRXWURPRGRRSHUDFLRQDO
1HVWHPRGRGHHQVDLRXPSHTXHQRSHGDoRGHILOPHUHWDQJXODUSRGHVHUXVDGR
FRPRFRUSRGHSURYDRTXDOpVXEPHWLGRDXPDFDUJD$VGLPHQV}HVGDVXSHUItFLH
GR ILOPH VmR GH PP [ PP $ FDUJD D VHU XWLOL]DGD QR H[SHULPHQWR p REWLGD HP
IXQomRGRYDORUGDHVSHVVXUDGRFRUSRGHSURYDVHJXQGRD(TXDomR
(2 Sbd 2 )
P=
3L
(11.4)
RQGH3pDFDUJDDSOLFDGDOEI6pDWHQVmRPi[LPDH[HUFLGDVREUHRFRUSRGHSURYD

SVLEpDODUJXUDGDDPRVWUDLQGpDHVSHVVXUDGDDPRVWUDLQH/pDGLVWkQFLD
HQWUHRVVXSRUWHVGDDPRVWUDLQ

$SyV D FRORFDomR GD FDUJD DSURSULDGD WHP LQtFLR D YDULDomR GD WHPSHUDWXUD D
XPD WD[D GH DTXHFLPHQWR FRQVWDQWH (VVD WD[D GH DTXHFLPHQWR SRGH VHU VXSHULRU
jTXHODXWLOL]DGDQRPpWRGR$670'&PLQGHYLGRDRIDWRGDVGLPHQV}HVGD
DPRVWUD VHUHP PXLWR SHTXHQDV $ SHTXHQD GLPHQVmR GD DPRVWUD SHUPLWH XPD
UiSLGDWURFDGHFDORUHFRQVHTXHQWHPHQWHRHTXLOtEULRWpUPLFRpDOFDQoDGR
3HOR PpWRGR GD GHWHUPLQDomR GD WHPSHUDWXUD GR LQtFLR GD WUDQVLomR RQVHW
LGHQWLILFDVHDWHPSHUDWXUDGHRFRUUrQFLDGDGHIOH[mRGRPDWHULDO)LJXUD
)LJXUD&XUYDGH70$QRPRGRIOH[mRGHXPPDWHULDOSROLPpULFRHPIXQomRGDWHPSHUDWXUD
11.2.7 Exemplos de aplicao

$R ORQJR GR WH[WR DOJXPDV DSOLFDo}HV GR 70$ Mi IRUDP FLWDGDV WDLV FRPR D
GHWHUPLQDomRGH
SWHPSHUDWXUDGHWUDQVLomRYtWUHD
SWHPSHUDWXUDGHIXVmRFULVWDOLQD
SWHPSHUDWXUDGHFULVWDOL]DomR
SFRHILFLHQWH GH H[SDQVmR WpUPLFD OLQHDU GH XP PDWHULDO HP XPD GDGD IDL[D GH
WHPSHUDWXUD
$OpP GHVVDV DSOLFDo}HV DLQGD SRGHP VHU GHVFULWDV RXWUDV PXLWR LPSRUWDQWHV
SDUDRHVWXGRGHPDWHULDLVSROLPpULFRV

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 '
IRUQHFHP R PyGXOR SRU LQWHUPpGLR GD UD]mR HQWUH D WHQVmR DSOLFDGD H D
GHIRUPDomRVRIULGDjWHPSHUDWXUDFRQVWDQWHWDQWRHPHQVDLRVGHH[WHQVmRFRPR
QRVGHFRPSUHVVmR2SURFHGLPHQWRGRVWHVWHVGHFRPSUHVVmRWHPDOJXPDVIDOKDV
2XVRGHGLIHUHQWHVFRQILJXUDo}HVGDVDPRVWUDVDIHWDDVUHVSRVWDV3RUH[HPSORRV
GDGRVREWLGRVDSDUWLUGHFRUSRVGHSURYDFLOtQGULFRVHUHWDQJXODUHVQmRSRGHPVHU
FRPSDUDGRV
2VPDWHULDLVSOiVWLFRVSRGHPVHUSURMHWDGRVFRPEDVHHPLQIRUPDo}HVRULXQGDV
GH HQVDLRV GH FRPSUHVVmR (QWUHWDQWR p QHFHVViULD D DSOLFDomR GH IDWRUHV GH
FRUUHODomR VHMD SHOD IRUPD RX DWp PHVPR HP IXQomR GR VHX HVWDGR ItVLFR (VWDV
GLIHUHQoDVSRGHULDPVHUFDUDFWHUL]DGDVSRUH[HPSORSHODUD]mRGH3RLVVRQDTXDO
PXLWDV YH]HV p GLIHUHQFLDGD SDUD GLYHUVRV SROtPHURV H HP GLIHUHQWHV UHJL}HV
YLVFRHOiVWLFDV
$SULQFLSDOGLVWLQomRHQWUHHQVDLRVGHFRPSUHVVmRSRU70$HRVFRQYHQFLRQDLVp
REVHUYDGD TXDQGR p IHLWD D XWLOL]DomR GH FDUJD FRQVWDQWH VRE D DomR GH XPD
GHWHUPLQDGD YDULDomR GH WHPSHUDWXUD (VWH PpWRGR p FDSD] GH GHVFUHYHU R
FRPSRUWDPHQWRYLVFRHOiVWLFRGRVPDWHULDLVHGHQWUHDVYDQWDJHQVVmRGHVWDFDGDVD
UDSLGH] H D SHTXHQD TXDQWLGDGH GH DPRVWUD QHFHVViULD SDUD R H[SHULPHQWR 2
PyGXORGH<RXQJQHVWHFDVRpREWLGRSRULQWHUPpGLRGD(TXDomR
E =
3PR 1 2
4H
) [x
1/ 2
+ 0,252 x + 0,1588 x 3 / 2 + 0,2245 x 2 + 0,3069 x 5 / 2 + 0,2980 x 3
(11.5)
VHQGR[REWLGRSHODUHODomR
x =
Rd
H
RQGH ( p R PyGXOR GH <RXQJ 3 p D FDUJD QRUPDO 5 p R UDLR GD SRQWD HVIpULFD GD
VRQGD+pDHVSHVVXUDGDDPRVWUDGpRFRPSULPHQWRGHSHQHWUDomRGDVRQGDHp
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
DPRUIRV H OLQHDUHV DSUHVHQWDP GLIHUHQWHV UD]}HV GH 3RLVVRQ HP IXQomR GH VHX
HVWDGR ItVLFR RX VHMD HP GLIHUHQWHV WHPSHUDWXUDV &RQWXGR D SULQFLSDO FRUUHomR
SDUHFHHVWDUUHODFLRQDGDjJHRPHWULDGDDPRVWUD8PDDPRVWUDDRVHUVXEPHWLGDD
XP HVIRUoR DSUHVHQWD XPD UHDomR TXH p IXQomR GH GRLV IDWRUHV EiVLFRV L VXD
JHRPHWULDHLLDIRUPDGDSRQWDGDVRQGDXWLOL]DGDQRH[SHULPHQWR$XWLOL]DomRGH

XPDSRQWDFLUFXODUHFKDWDSHUPLWHREVHUYDUDLQIOXrQFLDGDJHRPHWULDGDDPRVWUD
HP DOWR JUDX 7RPDQGR FRPR UHIHUrQFLD D OHL GD DomR H UHDomR REVHUYDVH QHVWDV
FLUFXQVWkQFLDVTXHDWHQVmRDSUHVHQWDGDSHODDPRVWUDQmRpDPHVPDHPWRGRVRV
SRQWRV GH FRQWDWR 3RUWDQWR D UHVSRVWD GR PDWHULDO SDVVD D VHU UHJLGD SHOD VXD
IRUPD
0XLWRV HVWXGRV WrP VLGR UHDOL]DGRV FRP R LQWXLWR GH FDUDFWHUL]DU D UHVSRVWD GH
GHWHUPLQDGDV IRUPDV GH DPRVWUD HP UHODomR D GLIHUHQWHV PRGRV GH DSOLFDomR GRV
HVIRUoRVRXVHMDGLIHUHQWHVSRQWDVGDVVRQGDVXWLOL]DGDVQDWUDQVPLVVmRGRHVIRUoR
$ DYDOLDomR GD UHVSRVWD HOiVWLFD FRP UHODomR j XWLOL]DomR GH XPD SRQWD GH IRUPD
HVIpULFDSRGHVHUXWLOL]DGDQDGHWHUPLQDomRGRPyGXORGH<RXQJ2XVRGHSRQWDV
HVIpULFDV p FDSD] GH DQXODU RV HIHLWRV GD JHRPHWULD GD DPRVWUD 1RWDVH TXH RV
HVIRUoRV UHDOL]DGRV SRU WDLV SRQWRV SURGX]HP UHVSRVWDV Pi[LPDV HP XPD UHJLmR
SUDWLFDPHQWH SRQWXDO QR FHQWUR GD VXSHUItFLH GH FRQWDWR (P RXWUDV SDODYUDV
REVHUYDVHDRFRUUrQFLDGHXPJUDGLHQWHGHIRUoDQDUHVSRVWDGRPDWHULDODRHVIRUoR
TXHWHPVHXPi[LPRORFDOL]DGRQRFHQWURGDDSOLFDomRGRHVIRUoR
([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 $SyV HVWD HWDSD VmR HVFROKLGDV WHPSHUDWXUDV TXH
DEUDQJHP WRGD D IDL[D GH DQiOLVH QDV TXDLV VmR PHGLGDV DV GHIRUPDo}HV UHODWLYDV
FRUUHVSRQGHQWHV 3RU H[HPSOR SDUD XPD WHPSHUDWXUDEDVH GH & SRGHP VHU
HVFROKLGDVDVWHPSHUDWXUDVGH&$VGLIHUHQoDVHQWUHDVDOWXUDV
OLGDV QHVWDV WHPSHUDWXUDV H D DOWXUD PHGLGD QD WHPSHUDWXUDEDVH IRUQHFHP D
GHIRUPDomRVRIULGDDFDGDWHPSHUDWXUDSDUDFDGDDTXHFLPHQWRUHDOL]DGR'HSRVVH
GDV GHIRUPDo}HV D FDGD WHPSHUDWXUD H XWLOL]DQGR D (TXDomR RV YDORUHV GH
PyGXORGH<RXQJSDUDFDGDWHPSHUDWXUDSRGHPVHUREWLGRV
$ )LJXUD DSUHVHQWD XP JUiILFR GH YDULDomR GH PyGXOR HP IXQomR GD
WHPSHUDWXUD SDUD XPD DPRVWUD SROtPHUR QR HVWDGR DPRUIR H QR HVWDGR
VHPLFULVWDOLQRREWLGRSRUPHLRGHDQiOLVHWHUPRPHFkQLFD

)LJXUD&XUYDVGHPyGXORHPIXQomRGDWHPSHUDWXUDSDUDXPSROtPHURDPRUIRHRXWURVHPLFULVWDOLQR
REWLGDVSRUPHLRGHDQiOLVHWHUPRPHFkQLFD
SVariao da Tg com o grau de cura

$ YDULDomR GD 7J FRP R JUDX GH FXUD SRGH VHU PRQLWRUDGD SRU DQiOLVH
WHUPRPHFkQLFD $ )LJXUD DSUHVHQWD FXUYDV GH H[SDQVmR HP IXQomR GD
WHPSHUDWXUDSDUDGXDVDPRVWUDVGHERUUDFKDYXOFDQL]DGDVQDPHVPDWHPSHUDWXUD
HPWHPSRVGLIHUHQWHVWW2EVHUYDVHTXHD7JDXPHQWDFRPRDXPHQWRGRJUDX
GHFXUD
)LJXUD&XUYDVGHH[SDQVmRHPIXQomRGDWHPSHUDWXUDSDUDGXDVDPRVWUDVGHERUUDFKDYXOFDQL]DGDV
QDPHVPDWHPSHUDWXUDGXUDQWHRVWHPSRVDWHEWVHQGRWW

11.3 Viscoelasticidade
$WpDTXLIRLDERUGDGRRFRQFHLWRGHPyGXORUHODFLRQDGRDRFRPSRUWDPHQWRHOiVWLFR
GRVPDWHULDLV9DPRVGLVFXWLUXPSRXFRPDLVVREUHRFRPSRUWDPHQWRPHFkQLFRGRV
PDWHULDLV
6yOLGRV SHUIHLWDPHQWH HOiVWLFRV TXDQGR VXEPHWLGRV D XPD GHIRUPDomR
DUPD]HQDP WRGD D HQHUJLD VRE D IRUPD GH HQHUJLD SRWHQFLDO 1D GHIRUPDomR GH
OtTXLGRVWRGDHQHUJLDXVDGDpGLVVLSDGDVREDIRUPDGHFDORU0DWHULDLVSROLPpULFRV
DSUHVHQWDP XP FRPSRUWDPHQWRYLVFRHOiVWLFRLQWHUPHGLiULRHQWUHVyOLGRHOtTXLGR
SDUWHGDHQHUJLDpDUPD]HQDGDHSDUWHpGLVVLSDGDVREDIRUPDGHFDORU
(P JHUDO RV SROtPHURV SRGHP H[LVWLU HP GLIHUHQWHV HVWDGRV PHFkQLFRV HP
IXQomRGDWHPSHUDWXUDHRXWHPSRpIiFLOLPDJLQDUTXHXPSOiVWLFRTXHDSUHVHQWD
XPD FHUWD ULJLGH] j WHPSHUDWXUD DPELHQWH SRGH WRUQDUVH XP PDWHULDO PDLV IOH
[tYHOVHVXEPHWLGRDXPDWHPSHUDWXUDPDLVHOHYDGD(VWHVHVWDGRVSRGHPVHUGLYL
GLGRVHPWLSRVSULQFLSDLV
S(VWDGRYtWUHRVyOLGRHOiVWLFROLQHDU
S(VWDGRHOiVWLFRFRPHODVWLFLGDGHUHWDUGDGDVyOLGRYLVFRHOiVWLFR
S(VWDGRHOiVWLFRFRPHODVWLFLGDGHLQVWDQWkQHDIOXLGRYLVFRHOiVWLFR
S(VWDGRYLVFRVRIOXLGRYLVFRVROLQHDU
$ )LJXUD PRVWUD XP GLDJUDPD GH GHIRUPDomR UHVSRVWD GH FDGD WLSR GH
FRPSRUWDPHQWRPHQFLRQDGRDFLPDTXDQGRXPDWHQVmRpDSOLFDGD)LJXUDD
PDQWLGDGXUDQWHXPGHWHUPLQDGRWHPSRHHQWmRUHWLUDGD2HVWDGRPHFkQLFRGH
FRPSRUWDPHQWRGHVyOLGRHOiVWLFROLQHDU)LJXUDEDSUHVHQWDXPDGHIRUPDomR
UHVSRVWDLQVWDQWkQHDTXHVHPDQWpPFRQVWDQWHGXUDQWHRWHPSRHPTXHDWHQVmRp
PDQWLGDHpWRWDOPHQWHUHFXSHUDGDSDUDDVGLPHQV}HVRULJLQDLVTXDQGRDWHQVmRp
UHWLUDGD1HVWHFDVRWHPRVTXHDXPDWHQVmRFRQVWDQWHDGHIRUPDomRUHVSRVWD
p FRQVWDQWH H DPEDV HVWmR UHODFLRQDGDV DWUDYpV GH XPD FRQVWDQWH GH
SURSRUFLRQDOLGDGHRPyGXORGRVyOLGR(
E=
o
o
(11.6)

)LJXUD5HSUHVHQWDomRHVTXHPiWLFDGRSHUILOGHWHQVmRDSOLFDGDHGHIRUPDomRVRIULGDD7HQVmR
DSOLFDGD+LVWyULDGHGHIRUPDomRFRUUHVSRQGHQWHSDUDEVyOLGRHOiVWLFROLQHDUFIOXLGRYLVFRVROLQHDUG
VyOLGRYLVFRHOiVWLFRHIOXLGRYLVFRHOiVWLFR
2FRPSRUWDPHQWRUHSUHVHQWDGRQD)LJXUDFpRGHXPIOXLGRYLVFRVROLQHDU
1RWH TXH QHVWH FDVR D GHIRUPDomR QmR p LQVWDQWkQHD HOD DXPHQWD JUDGXDOPHQWH
FRP R WHPSR HQTXDQWR D WHQVmR FRQVWDQWH p H[HUFLGD VREUH R PDWHULDO $SyV D
UHPRomR GD WHQVmR R IOXLGR PDQWpPVH GHIRUPDGR QmR UHFXSHUDQGR VXDV
GLPHQV}HVRULJLQDLV,VWRVLJQLILFDTXHGXUDQWHDDSOLFDomRGHXPDWHQVmRFRQVWDQWH

RFRUUH XPD YDULDomR OLQHDU GD GHIRUPDomR o WD[D GH GHIRUPDomR

UHODFLRQDGDV HQWUH VL SRU XPD FRQVWDQWH GH SURSRUFLRQDOLGDGH D YLVFRVLGDGH GR
IOXLGR
o
o
(11.7)
$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 termodinmicomecnica (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
E=
o
o
(11.10)

HQWmRDGHIRUPDomRUHVSRVWDSRGHVHUHVFULWDFRPR
= E o sen ( t )
(11.11)
3DUDXPFRUSRGHFRPSRUWDPHQWRYLVFRVRLGHDODWHQVmRUHVSRVWDWDPEpPVHUi
GRWLSRVHQRLGDOSRUpPHVWDUiRIRUDGHIDVHFRPDGHIRUPDomR3DUDIOXLGRVD
WHQVmRHDWD[DGHGHIRUPDomRHVWmRUHODFLRQDGDVHQWUHVLSHODYLVFRVLGDGH
(11.12)
HQWmR
=
&RPRDGHIRUPDomRDSOLFDGDp
=
(11.13)
= o sen ( t )HQWmR
d
= o cos( t )
dt
(11.14)
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)

(VWD ~OWLPD HTXDomR PRVWUD TXH D WHQVmR UHVSRVWD SRGH VHU UHVROYLGD HP GXDV
FRPSRQHQWHV
S o sen t cos TXH p D FRPSRQHQWH HP IDVH FRP D GHIRUPDomR H HVWi
UHODFLRQDGDjHQHUJLDHOiVWLFDDUPD]HQDGD
S o cos t sen TXHpDFRPSRQHQWHRIRUDGHIDVHFRPDGHIRUPDomRH
HVWiUHODFLRQDGDjHQHUJLDYLVFRVDGLVVLSDGD
( )
( )
'LYLGLQGRVHFDGDXPDGHVVDVFRPSRQHQWHVGDWHQVmRUHVSRVWDSHODGHIRUPDomR
VHQRLGDODSOLFDGDREWrPVHGXDVFRPSRQHQWHVHPWHUPRVGHPyGXOR
E =
H
E =
o sen ( t )
cos
o sen ( t )
(11.18)
o cos( t )
sen
o sen ( t )
(11.19)
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
tan =
E
tangente de perda
(11.21)
(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
SRWHQFLDO Pi[LPD DUPD]HQDGD GXUDQWH R FLFOR (VWD UHODomR p PXLWR ~WLO QD
FDUDFWHUL]DomR GH VLVWHPDV SROLPpULFRV $VVLP PDWHULDLV PDLV UtJLGRV LUmR

DSUHVHQWDU YDORUHV GH WDQ PHQRUHV H GR PHVPR PRGR PDWHULDLV PDLV IOH[tYHLV
LUmRDSUHVHQWDUYDORUHVGHWDQPDLRUHV
$V WUrV JUDQGH]DV GHILQLGDV DFLPD VmR HP JHUDO GDGDV HP IXQomR GD
WHPSHUDWXUD RX GD IUHTrQFLD HP XP HQVDLR GH '07$ 3RGHVH REWHU HP XP
PHVPRJUiILFRDVFXUYDVGH((HWDQ
$ )LJXUD UHSUHVHQWD DV IXQo}HV VHQRLGDLV GD GHIRUPDomR DSOLFDGD H GD
WHQVmR UHVSRVWD SDUD PDWHULDLV D HOiVWLFRV OLQHDUHV E YLVFRVRV OLQHDUHV H F
YLVFRHOiVWLFRV
)LJXUD5HSUHVHQWDomRGDVIXQo}HVVHQRLGDLVGDGHIRUPDomRDSOLFDGDHGDWHQVmRUHVSRVWDSDUD

PDWHULDLVDHOiVWLFRVOLQHDUHVEYLVFRVRVOLQHDUHVHFYLVFRHOiVWLFRV
3DUDPHOKRUFRPSUHHQGHURVLJQLILFDGRGHGHIRUPDomRVHQRLGDOYDPRVFRPSDUDU
RPRYLPHQWRTXHRFRUUHHPHQVDLRVWUDQVLWyULRHGLQkPLFRSDUDXPDGHIRUPDomRGR
WLSRWUDomR&RPRMiIRLYLVWRDQWHULRUPHQWHSDUDXPHQVDLRGHWUDomRWUDQVLWyULRR
FRUSRpGHIRUPDGRXPD~QLFDYH]HDWHQVmRGHVHQYROYLGDpPHGLGD)LJXUDD
(PXPPHVPRHQVDLRGHWUDomRSRUpPGLQkPLFR)LJXUDERSRQWRPyYHOID]
XPPRYLPHQWRGHYDLHYHP

11.4.2 Instrumentao
([LVWHP KRMH QR PHUFDGR GLYHUVRV HTXLSDPHQWRV FRPHUFLDLV FRP FDUDFWHUtVWLFDV
GLVWLQWDV 7DLV HTXLSDPHQWRV SRGHP YDULDU SULQFLSDOPHQWH FRP UHODomR j IDL[D GH
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11.4.3 Transies secundrias
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D
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XPD WUDQVLomR WHUPRGLQkPLFD GH D RUGHP H D 7P GH D RUGHP $PEDV HVWmR
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UHOD[DomR SULPiULD 0RYLPHQWRV PHQRV VLJQLILFDWLYRV TXH RFRUUHP QD PROpFXOD
SULQFLSDOPHQWH D WHPSHUDWXUDV DEDL[R GD 7J VmR GHQRPLQDGRV UHOD[Do}HV
VHFXQGiULDV $LQGD QD )LJXUD p SRVVtYHO REVHUYDU D 7J QD TXDO RFRUUH XP
PRYLPHQWRVLJQLILFDWLYRGDVFDGHLDVRTXDOSURYRFDXPSLFRDFHQWXDGRHPWRUQRGH
R& (QTXDQWR TXH PRYLPHQWRV PDLV GLVFUHWRV GH UHOD[Do}HV VHFXQGiULDV VmR
REVHUYDGRVHPSLFRVPDLVGLVFUHWRVHPWRUQRGHHR&
'H PRGR UHVXPLGR DV WUDQVLo}HV TXH RFRUUHP QDV PROpFXODV SRGHP VHU
GLYLGLGDV HP WUDQVLo}HV TXH RFRUUHP QD IDVH DPRUID H WUDQVLo}HV TXH RFRUUHP QD
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DOWD SDUD D PDLV EDL[D WHPSHUDWXUD (VWDV WUDQVLo}HV VmR PHOKRU REVHUYDGDV SHORV
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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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3ROLHWLOHQR
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3ROLIOXRUHWRGH
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3ROLy[LGRGHHWLOHQR
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3ROLSURSLOHQR
[-CH2-CH(CH3)-]n

3ROLFDSURODFWDPD
[-NH-(CH2)5-(CO)-]n

11.4.4 Utilizao da Equao de Arrhenius

&RPR Mi PHQFLRQDGR QR LQtFLR GHVWH FDStWXOR R YDORU GD WUDQVLomR REVHUYDGD QR
HVSHFWUR GH UHOD[DomR REWLGR YDULD HPIXQomRGDIUHTrQFLDXWLOL]DGDQRHQVDLRH
SRULVVRID]VHQHFHVViULRPHQFLRQDUDOpPGHRXWUDVFRLVDVHPTXHIUHTrQFLDGH
HQVDLRDFXUYDIRLREWLGD3DUDIUHTrQFLDVGHHQVDLRPDLVHOHYDGDVDVWHPSHUDWXUDV
GH WUDQVLomR REVHUYDGDV QDV FXUYDV GR HVSHFWUR GH UHOD[DomR GHVORFDPVH SDUD
YDORUHV PDLV DOWRV FRPR SRGH VHU REVHUYDGR QD )LJXUD (VWH GHVORFDPHQWR
QmRRFRUUHGHPRGRDUELWUiULRHQHPpSDGUmRSDUDWRGRVRVPDWHULDLVHOHpIXQomR
GD HQHUJLD HQYROYLGD QR SURFHVVR GH WUDQVLomR $VVLP GH SRVVH GRV YDORUHV GH
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log f = log f o
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11.4.5 Correlao tempo-temperatura

$VVLPFRPRSDUDRVHQVDLRVPHFkQLFRVRVHQVDLRVGLQkPLFRPHFkQLFRVSRGHPVHU
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GR WHPSR W $ )LJXUD DSUHVHQWD XPD FXUYD WtSLFD GH PyGXOR HP
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3DUD PHOKRU HQWHQGHU HVWH ~OWLPR IHQ{PHQR YDPRV WRPDU FRPR H[HPSOR XPD
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GRPDWHULDOWHQGHDFHGHUFRPDUHGXomRGDIUHTrQFLDGRHQVDLR3DUDIUHTrQFLDV
GHHQVDLRVPXLWRDOWDVRFLFORGDDomRLPSRVWDpPXLWRUiSLGRHDDPRVWUDQmRWHP
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SDUD UHOD[DU H VXD UHVSRVWD j VROLFLWDomR PHFkQLFD SRGHUi VHU REVHUYDGD LVWR p R
YDORU GH PyGXOR REVHUYDGR VHUi PHQRU 3DUD HQWHQGHU R VHQWLGR GH FLFOR GD DomR
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GH 7J XP SRXFR DEDL[R GD WHPSHUDWXUD DPELHQWH DSUHVHQWDUmR XPD TXHGD
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$SHUPLVVLYLGDGHGLHOpWULFDFRPSOH[D SRGHVHUPHGLGDDSDUWLUGDYDULDomRQD
DPSOLWXGHHVHRDWUDVRGDIDVHHQWUHDYROWDJHPDSOLFDGDHDFRUUHQWHLQGX]LGDp
GHWHUPLQDGR)LJXUDHQWmR SRGHVHUUHVROYLGDHPGXDVFRPSRQHQWHV
S$FRQVWDQWHGLHOpWULFDGHDUPD]HQDPHQWR
S$FRQVWDQWHGLHOpWULFDGHSHUGD

$QiOLVH'LHOpWULFDRX7HUPRGLHOpWULFD'($RX'(7$
)LJXUD'LDJUDPDHVTXHPiWLFRDGHXPDFpOXODGHPHGLGDHEGRFRPSRUWDPHQWRGDYROWDJHP

DSOLFDGDHGDFRUUHQWHUHVSRVWDQR'(7$
5HVXPLQGR DV TXDWUR SURSULHGDGHVFKDYH TXH VmR PHGLGDV SHOR '(7$ VmR
SHUPLVVLYLGDGHIDWRUGHSHUGDFRQGXWLYLGDGHL{QLFDHIDWRUGHGLVVLSDomR
$SHUPLVVLYLGDGHWDPEpPFKDPDGDGHFRQVWDQWHGLHOpWULFDGHDUPD]HQDPHQWRp
SURSRUFLRQDOjFDSDFLWkQFLDTXHpDFDSDFLGDGHGRPDWHULDOGHDUPD]HQDUFDUJD

HOpWULFD (VWD p XPD PHGLGD GD IDFLOLGDGH FRP TXH RV GLSRORV QR SROtPHUR VmR
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

)LJXUD5HSUHVHQWDomRHVTXHPiWLFDGRFRPSRUWDPHQWRGRVIDWRUHVGHDUPD]HQDPHQWRHSHUGD
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
$FRQVWDQWHGLHOpWULFDSRGHVHUFRQVLGHUDGDFRPRHTXLYDOHQWHjFRPSOLkQFLD
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

$PEDV DV WpFQLFDV UHVSRQGHP GH PRGR VLPLODU D XPD YDULDomR QD IUHTrQFLD
PHGLGD 4XDQGR D IUHTrQFLD p DXPHQWDGD DV WUDQVLo}HV H UHOD[Do}HV TXH VmR
REVHUYDGDVQDDPRVWUDDSDUHFHPDWHPSHUDWXUDVPDLVHOHYDGDV,VWRpLOXVWUDGRQD
)LJXUDTXHPRVWUDXPDDQiOLVHGHSROLWHUHIWDODWRGHHWLOHQR2SLFRGHSHUGD
UHSUHVHQWDQGRDWUDQVLomRYtWUHDIRLPHGLGRSRU'07$H'(7$DYiULDVIUHTrQFLDV
HQWUH+]HN+]
)LJXUD&RPSDUDomRGDVFXUYDVREWLGDVSRU'07$H'(7$
2Pi[LPRGRSLFR7Pi[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 SROLPHWDFULODWR GH DOTXLOD

$PEDV DV WpFQLFDV '07$ 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
QRSROLPHWDFULODWRGHPHWLOD300$SROLPHWDFULODWRGHHWLOD3(0$HSROLPHWDFULODWRGHWEXWLOD
3W%0$6tPERORVEUDQFRVUHSUHVHQWDPPHGLGDVUHDOL]DGDVSRUPpWRGRGLHOpWULFRHVtPERORVSUHWRVSDUD
PHGLGDVGLQkPLFRPHFkQLFDV
'LIHUHQoDVEiVLFDVQDVDQiOLVHVGH'07$H'(7$VmRFRPSDUDGDVQR4XDGUR
4XDGUR'LIHUHQoDVEiVLFDVQDVDQiOLVHVGH'07$H'(7$
&DUDFWHUtVWLFD
(VFDODGHGHWDOKHVHVWUXWXUDLV
'HWHFomRGHHVWUXWXUDVHPXPD
PLVWXUDFRPGRPtQLRVPXLWR
SHTXHQRV
$FRPSDQKDPHQWRGHUHDo}HVTXH
RFRUUHPQRV~OWLPRVHVWiJLRVGH
FXUDGHXPVLVWHPDWHUPRUUtJLGR
7LSRGHDPRVWUD
7RPDGDGHIUHTrQFLDQDIDL[DGH
D+]
'(7$
'07$
QP
0HGHDSURSULHGDGHHPQtYHO
PDFURVFySLFR
6,0
$SDUrQFLDGHFRPSOHWD
PLVFLELOLGDGH
6,0
12
3ySDVWDVyOLGRVHOtTXLGRV
8PDPHVPDDPRVWUDSDUDXPD 6yOLGRVHPJHUDO

DPSODIDL[DGH WUDQVLomR
/LPLWDo}HVPHFkQLFDV
VyOLGROtTXLGR
GpFDGDV
GpFDGDV

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~QLFDFRQILJXUDomRGRWLSRSHQWHGHHOHWURGRV
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
HVWiDVVRFLDGRDRHVWDGRERUUDFKRVRDFLPDGD7JGRSROtPHUR2VHJXQGRWLSR
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

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 SROLpWHU 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 $V SURSULHGDGHV GLHOpWULFDV VXUJHP D SDUWLU GRV VHJXLQWHV
FRPSRQHQWHV D SHUGD GH GLSROR QRUPDO D SDUWLU GH FDGHLDV GD ERUUDFKD
YXOFDQL]DGD FRP HQ[RIUH E SHUGDV GH FRQGXWLYLGDGH GHYLGR D FDPLQKRV GH
FRQGXomR GLUHWD GDV SDUWtFXODV GH QHJUR GH IXPR OLJDGDV QD PDWUL] SROLPpULFD F
SHUGDV GH 0D[ZHOO:DJQHU GHYLGR j FDSDFLGDGH GDV SDUWtFXODV GH QHJUR GH IXPR
FRQGX]LUHP HP XP PHLR ERUUDFKRVR QmRFRQGXWRU G SHUGDV HVWUXWXUDLV
FDUDWHUL]DGDVSRUXPDSHUGDTXHpLQGHSHQGHQWHGDWHPSHUDWXUDHGDIUHTrQFLDD
XPDGDGDFRPSRVLomRGHQHJURGHIXPR$VSHUGDVGRWLSRGVmRXPDIXQomRGD
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

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

DQiOLVHV )LJXUD 2 SLFR GH SHUGD D PDLV DOWD WHPSHUDWXUD SLFR HVWi
UHODFLRQDGRDRSURFHVVRGHWUDQVLomRYtWUHDLVWRpFRQILUPDGRSRUPHGLGDVGH'6&
2RXWURSLFRUHOD[DomR TXHDSDUHFHDWHPSHUDWXUDPDLVEDL[DVXJHUHTXHH[LVWH
XP SURFHVVR GH UHOD[DomR DWLYR QR HVWDGR YtWUHR 1mR p LPHGLDWDPHQWH yEYLR TXDO
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Caracterização de Polímeros - Bete&#39;s

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Caracterização de Polímeros - Bete&#39;s

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E-papers Servios Editoriais Ltda., 2001.

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SClassificao quanto rotao dos tomos da cadeia em torno de

SClassificao quanto ao encadeamento das unidades monomricas

SClassificao condensao-adio (segundo W. H. Carothers)

H2N-R-N2H + HO2 C-R-CO2H

Polmeros de polipeptdeos que ocorrem naturalmente

HO-R-OH + HO2 C-R-CO2H

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SClassificao quanto estrutura qumica

SClassificao quanto variedade de meros que compem a cadeia

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Para polmeros de adio

Para polmeros de condensao

(energia livre de mistura)

Gsol = x1G10 + x2G20 + x3G30 + .....

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Gexc = Gmis - G (ideal)

Sexc = Smis - S (ideal)

2.3 Processo de dissoluo de um polmero

2.4 Afinidade termodinmica entre um solvente e um polmero

2.4.3 Presso de inchamento

2.5 Fatores que afetam a dissoluo e inchamento dos polmeros

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Caracterização de Polímeros - Bete's

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