521:
235:
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124:, but at present there is little sign of acceptance of this change. The area of physical organic chemistry which deals with such relations is commonly referred to as 'linear free-energy relationships'.
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A typical LFER relation for predicting the equilibrium concentration of a compound or solute in the vapor phase to a condensed (or solvent) phase can be defined as follows (following
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Abraham MH, Ibrahim A, Zissimos AM, Zhao YH, Comer J, Reynolds DP (October 2002). "Application of hydrogen bonding calculations in property based drug design".
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can be determined. Free energy relationships are often used to calculate equilibrium constants since they are experimentally difficult to determine.
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with the logarithm of the rate or equilibrium constant for a related series of reactions. Free energy relationships establish the extent at which
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Poole CF, Atapattu SN, Poole SK, Bell AK (October 2009). "Determination of solute descriptors by chromatographic methods".
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516:{\displaystyle \log \mathrm {SP} =c+e\mathrm {E} +s\mathrm {S} +a\mathrm {A} +b\mathrm {B} +v\mathrm {V} }
420:= the contribution from hydrogen-bond acidity to the transfer of the solute from air to the aerosol phase.
230:{\displaystyle \log \mathrm {SP} =c+e\mathrm {E} +s\mathrm {S} +a\mathrm {A} +b\mathrm {B} +l\mathrm {L} }
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The most common form of free-energy relationships are linear free-energy relationships (LFER). The
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descriptors representing the complementary properties of the compounds. Specifically,
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of a series of catalysts and the reaction rate constant for a reaction on which the
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Relation between the equilibrium/reaction rate constants of two chemical reactions
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Similarly, the correlation of solvent–solvent partition coefficients as
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predicts the equilibrium constant or reaction rate of a reaction from a
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384:= the contribution from cavity formation and dispersion interactions;
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by virtue of its capacity for orientation and induction interactions;
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410:= the contribution from hydrogen-bond basicity (because a basic
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is an example of a quadratic free-energy relationship (QFER).
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346:= the ability of a solute to stabilize a neighbouring
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The complementary system constants are identified as
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116:has suggested that this name should be replaced by
759:Bradley JC, Abraham MH, Acree WE, Lang AS (2015).
640:Lassila JK, Zalatan JG, Herschlag D (2011-06-15).
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256:, anesthetic potency, etc. The lowercase letters (
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404:= the contribution from dipole-type interactions;
390:= the contribution from interactions with solute
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761:"Predicting Abraham model solvent coefficients"
534:in cubic centimeters per mole divided by 100.
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589:Quantitative structure–activity relationship
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532:McGowan's characteristic molecular volume
414:will interact with an acidic solute); and
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369:= the solute's effective hydrogen-bond
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59:of a reaction, and in combination with
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658:10.1146/annurev-biochem-060409-092741
134:LFER solvent coefficients (data page)
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819:Compendium of Chemical Terminology
616:Compendium of Chemical Terminology
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248:related property, such as an
584:Bell–Evans–Polanyi principle
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824:linear free-energy relation
621:linear free-energy relation
544:Brønsted catalysis equation
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72:Brønsted catalysis equation
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852:Physical organic chemistry
564:Grunwald–Winstein equation
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21:physical organic chemistry
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765:Chemistry Central Journal
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356:= the solute's effective
252:or absorption constant,
25:free-energy relationship
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629:10.1351/goldbook.L03551
726:Analytica Chimica Acta
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92:reaction type constant
37:reaction rate constant
569:Yukawa–Tsuno equation
559:Swain–Lupton equation
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29:Gibbs energy relation
691:Drug Discovery Today
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88:substituent constant
41:equilibrium constant
76:ionization constant
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65:reaction mechanism
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132:Main article:
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100:polarisability
82:operates. The
63:experiments a
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140:M.H. Abraham
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120:Gibbs energy
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31:relates the
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392:n-electrons
320:-hexadecane
246:free-energy
841:Categories
595:References
340:-alkanes).
250:adsorption
847:Solutions
442:
156:
33:logarithm
797:25798192
746:19786169
711:12546895
676:21513457
538:See also
371:basicity
282:sorption
244:is some
122:relation
104:basicity
80:catalyst
53:breakage
788:4369285
667:3418923
412:sorbent
361:acidity
278:aerosol
118:linear
795:
785:
771:: 12.
744:
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664:
526:where
426:log SP
348:dipole
306:solute
304:) are
240:where
106:. The
94:. The
90:and a
814:IUPAC
611:IUPAC
363:; and
334:E = 0
254:log K
114:IUPAC
35:of a
793:PMID
742:PMID
707:PMID
672:PMID
394:and
336:for
102:and
49:bond
23:, a
828:doi
826:".
783:PMC
773:doi
734:doi
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699:doi
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625:doi
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530:is
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153:log
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292:,
288:,
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268:,
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260:,
242:SP
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713:.
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627::
528:V
510:V
506:v
503:+
499:B
495:b
492:+
488:A
484:a
481:+
477:S
473:s
470:+
466:E
462:e
459:+
456:c
453:=
449:P
446:S
418:b
408:a
402:s
398:;
388:e
382:l
373:.
367:B
354:A
344:S
338:n
332:(
326:E
318:n
313:L
302:L
298:B
294:A
290:S
286:E
274:l
270:b
266:a
262:s
258:e
224:L
220:l
217:+
213:B
209:b
206:+
202:A
198:a
195:+
191:S
187:s
184:+
180:E
176:e
173:+
170:c
167:=
163:P
160:S
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