251:
211:
called aprotic. H-bond donor ability is classified on a scale (α). Protic solvents can solvate solutes that can accept hydrogen bonds. Similarly, solvents that can accept a hydrogen bond can solvate H-bond-donating solutes. The hydrogen bond acceptor ability of a solvent is classified on a scale (β). Solvents such as water can both donate and accept hydrogen bonds, making them excellent at solvating solutes that can donate or accept (or both) H-bonds.
159:
27:
246:
solvent molecules leads to a greater enthalpic penalty for cavity formation. Next, a particle of solute must separate from the bulk. This is enthalpically unfavorable since solute-solute interactions decrease, but when the solute particle enters the cavity, the resulting solvent-solute interactions are enthalpically favorable. Finally, as solute mixes into solvent, there is an entropy gain.
179:(or hydration shell in the case of water) around each particle of solute. The solvent molecules in the immediate vicinity of a solute particle often have a much different ordering than the rest of the solvent, and this area of differently ordered solvent molecules is called the cybotactic region. Water is the most common and well-studied polar solvent, but others exist, such as
272:) times the change in entropy. Gases have a negative entropy of solution, due to the decrease in gaseous volume as gas dissolves. Since their enthalpy of solution does not decrease too much with temperature, and their entropy of solution is negative and does not vary appreciably with temperature, most gases are less soluble at higher temperatures.
382:. Many host molecules have a hydrophobic pore that readily encapsulates a hydrophobic guest. These interactions can be used in applications such as drug delivery, such that a hydrophobic drug molecule can be delivered in a biological system without needing to covalently modify the drug in order to solubilize it. Binding constants for
175:
charge while the part with less electron density will experience a partial positive charge. Polar solvent molecules can solvate polar solutes and ions because they can orient the appropriate partially charged portion of the molecule towards the solute through electrostatic attraction. This stabilizes the system and creates a
315:
Strong solvent–solute interactions make the process of solvation more favorable. One way to compare how favorable the dissolution of a solute is in different solvents is to consider the free energy of transfer. The free energy of transfer quantifies the free energy difference between dilute solutions
53:
interact strongly with a solvent, and the strength and nature of this interaction influence many properties of the solute, including solubility, reactivity, and color, as well as influencing the properties of the solvent such as its viscosity and density. If the attractive forces between the solvent
412:
As computer power increased, it became possible to try and incorporate the effects of solvation within a simulation and the simplest way to do this is to surround the molecule being simulated with a "skin" of solvent molecules, akin to simulating the molecule within a drop of solvent if the skin is
174:
is the most important factor in determining how well it solvates a particular solute. Polar solvents have molecular dipoles, meaning that part of the solvent molecule has more electron density than another part of the molecule. The part with more electron density will experience a partial negative
245:
Solvation involves multiple steps with different energy consequences. First, a cavity must form in the solvent to make space for a solute. This is both entropically and enthalpically unfavorable, as solvent ordering increases and solvent-solvent interactions decrease. Stronger interactions among
210:
Hydrogen bonding among solvent and solute molecules depends on the ability of each to accept H-bonds, donate H-bonds, or both. Solvents that can donate H-bonds are referred to as protic, while solvents that do not contain a polarized bond to a hydrogen atom and cannot donate a hydrogen bond are
165:
at daylight (top row) and UV-light (second row) in different solvents. From left to right: 1. Water, 2. Methanol, 3. Ethanol, 4. Acetonitrile, 5. Dimethylformamide, 6. Acetone, 7. Ethylacetate, 8. Dichlormethane 9. n-Hexane, 10. Methyl-tert-Butylether, 11. Cyclohexane, 12. Toluene. Photographer:
54:
and solute particles are greater than the attractive forces holding the solute particles together, the solvent particles pull the solute particles apart and surround them. The surrounded solute particles then move away from the solid solute and out into the solution. Ions are surrounded by a
275:
Enthalpy of solvation can help explain why solvation occurs with some ionic lattices but not with others. The difference in energy between that which is necessary to release an ion from its lattice and the energy given off when it combines with a solvent molecule is called the
154:
Which of these forces are at play depends on the molecular structure and properties of the solvent and solute. The similarity or complementary character of these properties between solvent and solute determines how well a solute can be solvated by a particular solvent.
242:(multiplied by the absolute temperature) is a negative value, or that the Gibbs energy of the system decreases. A negative Gibbs energy indicates a spontaneous process but does not provide information about the rate of dissolution.
292:
that results when the ion dissolves. The introduction of entropy makes it harder to determine by calculation alone whether a substance will dissolve or not. A quantitative measure for solvation power of solvents is given by
319:
In general, thermodynamic analysis of solutions is done by modeling them as reactions. For example, if you add sodium chloride to water, the salt will dissociate into the ions sodium(+aq) and chloride(-aq). The
132:. The consideration of the units makes the distinction clearer. The typical unit for dissolution rate is mol/s. The units for solubility express a concentration: mass per volume (mg/mL), molarity (mol/L), etc.
358:
occurs spontaneously, in part because of a favorable change in the interactions between the protein and the surrounding water molecules. Folded proteins are stabilized by 5-10 kcal/mol relative to the
397:
Due to the importance of the effects of solvation on the structure of macromolecules, early computer simulations which attempted to model their behaviors without including the effects of solvent (
1023:
Jiang D.; Urakawa A.; Yulikov M.; Mallat T.; Jeschke G.; Baiker A. (2009). "Size selectivity of a copper metal-organic framework and origin of catalytic activity in epoxide alcoholysis".
288:
value means that solvation will not occur. It is possible that an ion will dissolve even if it has a positive enthalpy value. The extra energy required comes from the increase in
203:, although other solvent scales are also used to classify solvent polarity. Polar solvents can be used to dissolve inorganic or ionic compounds such as salts. The
334:
Recent simulation studies have shown that the variation in solvation energy between the ions and the surrounding water molecules underlies the mechanism of the
401:) could yield poor results when compared with experimental data obtained in solution. Small molecules may also adopt more compact conformations when simulated
354:
and proteins, in aqueous solutions influences the formation of heterogeneous assemblies, which may be responsible for biological function. As another example,
1404:
218:, which is a change in color due to solvent polarity. This phenomenon illustrates how different solvents interact differently with the same solute. Other
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of a solute in two different solvents. This value essentially allows for comparison of solvation energies without including solute-solute interactions.
563:
109:. The concept of the solvation interaction can also be applied to an insoluble material, for example, solvation of functional groups on a surface of
86:
642:
Taft R. W., Kamlet M. J. (1976). "The solvatochromic comparison method. 1. The .beta.-scale of solvent hydrogen-bond acceptor (HBA) basicities".
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of the solution is decreased, compared to the Gibbs energy of the separated solvent and solid (or gas or liquid). This means that the change in
615:
Taft R. W., Kamlet M. J. (1976). "The solvatochromic comparison method. 2. The .alpha.-scale of solvent hydrogen-bond donor (HBD) acidities".
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is the solution enthalpy minus the enthalpy of the separate systems, whereas the entropy of solution is the corresponding difference in
903:
Bonn Mischa; et al. (2012). "Interfacial Water
Facilitates Energy Transfer by Inducing Extended Vibrations in Membrane Lipids".
472:
M. Andreev; J. de Pablo; A. Chremos; J. F. Douglas (2018). "Influence of Ion
Solvation on the Properties of Electrolyte Solutions".
350:) is important for many biological structures and processes. For instance, solvation of ions and/or of charged macromolecules, like
312:, which are readily hydrolyzed to form insoluble (hydrous) oxides. As these are solids, it is apparent that they are not solvated.
204:
207:
of a solution depends on the solvation of its ions. Nonpolar solvents cannot solvate ions, and ions will be found as ion pairs.
150:
The van der Waals forces, which consist of dipole–dipole, dipole–induced dipole, and induced dipole–induced dipole interactions.
58:. Solvation is the process of reorganizing solvent and solute molecules into solvation complexes and involves bond formation,
602:
548:
516:
696:
M. Andreev; A. Chremos; J. de Pablo; J. F. Douglas (2017). "Coarse-Grained Model of the
Dynamics of Electrolyte Solutions".
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side chains exposed to water by burying them in the center of a folded protein is a driving force related to solvation.
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304:, or the charge density, resulted in more solvation, this does not stand up to scrutiny for ions like iron(III) or
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value for the enthalpy change of solution corresponds to an ion that is likely to dissolve, whereas a high
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Eric V. Anslyn; Dennis A. Dougherty (2006). Modern
Physical Organic Chemistry. University Science Books.
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and intramolecular electrostatic interactions which would be dampened in the presence of a solvent.
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for this dissociation can be predicted by the change in Gibbs energy of this reaction.
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include conformational or isomeric preferences and changes in the acidity of a solute.
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and solvation, including entropy effects related to changes in the solvent structure.
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Gutmann V (1976). "Solvent effects on the reactivities of organometallic compounds".
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Steed, J. W. and Atwood, J. L. (2013) Supramolecular
Chemistry. 2nd ed. Wiley.
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572:, 2nd ed. (the "Gold Book") (1997). Online corrected version: (2006–) "
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Although early thinking was that a higher ratio of a cation's ion charge to
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The solvation process will be thermodynamically favored only if the overall
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97:. In the solvated state, an ion or molecule in a solution is surrounded or
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Hydration affects electronic and vibrational properties of biomolecules.
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Association of molecules of a solvent with molecules or ions of a solute
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One example of a solvated MOF, where partial dissolution is described.
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is used to estimate Gibbs free energy of solvation of a gaseous ion.
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stronger intramolecular interactions in the folded protein structure
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Solvation involves different types of intermolecular interactions:
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790:"Forces contributing to the conformational stability of proteins"
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268:) is the change in enthalpy minus the product of temperature (in
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process and is quantified by its rate. Solubility quantifies the
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by solvent molecules. Solvated species can often be described by
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state achieved when the rate of dissolution equals the rate of
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954:(2nd ed.). Harlow, England: Prentice Hall. p. 320.
511:. Boston, Massachusetts: Pearson Prentice Hall. p. 734.
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definition, solvation is an interaction of a solute with the
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93:, which leads to stabilization of the solute species in the
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Molecular modelling : principles and applications
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Pace, CN; Shirley, BA; McNutt, M; Gajiwala, K (1996).
66:. Solvation of a solute by water is called hydration.
586:
1405:
List of boiling and freezing information of solvents
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1056:"Transfer Free Energy and the Hydrophobic Effect"
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226:Solvation energy and thermodynamic considerations
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341:
199:. Polar solvents are often found to have a high
393:Importance of solvation in computer simulations
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166:Armin KĂĽbelbeck, CC-BY-SA, Wikimedia Commons
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733:"Polyelectrolyte association and solvation"
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73:compounds depends on a competition between
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363:due to a combination of solvation and the
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136:Solvents and intermolecular interactions
116:Solvation is, in concept, distinct from
30:A sodium ion solvated by water molecules
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994:(3 vol. ed.). Amsterdam: Elsevier.
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386:depend on the polarity of the solvent.
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854:Mashaghi Alireza; et al. (2012).
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214:Some chemical compounds experience
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731:A. Chremos; J. F. Douglas (2018).
569:Compendium of Chemical Terminology
264:. The solvation energy (change in
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992:The Chemical Physics of Solvation
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120:. Solvation or dissolution is a
990:; et al., eds. (1985–88).
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737:The Journal of Chemical Physics
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37:describes the interaction of a
1053:Serafin, J.M. (October 2003).
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509:Chemistry - California Edition
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1:
1025:Chemistry: A European Journal
683:10.1016/S0010-8545(00)82045-7
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342:Macromolecules and assemblies
1395:Inorganic nonaqueous solvent
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807:10.1096/fasebj.10.1.8566551
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405:; this is due to favorable
371:. Minimizing the number of
278:enthalpy change of solution
81:Distinction from solubility
56:concentric shell of solvent
10:
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1380:Acid dissociation constant
407:van der Waals interactions
18:
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948:Leach, Andrew R. (2001).
537:Chemistry of the Elements
535:; Earnshaw, Alan (1997).
346:Solvation (specifically,
710:10.1021/acs.jpcb.7b04297
486:10.1021/acs.jpcb.8b00518
19:Not to be confused with
1345:Solubility table (data)
1212:Apparent molar property
582:10.1351/goldbook.S05747
380:host–guest complexation
378:Solvation also affects
147:Ion–dipole interactions
1310:Total dissolved solids
1305:Solubility equilibrium
1230:and related quantities
1037:10.1002/chem.200901510
507:Cambell, Neil (2006).
434:Solubility equilibrium
167:
31:
1410:Partition coefficient
1390:Polar aprotic solvent
541:Butterworth-Heinemann
533:Greenwood, Norman N.
161:
29:
1325:Enthalpy of solution
1252:Volume concentration
1247:Number concentration
384:host–guest complexes
322:equilibrium constant
258:enthalpy of solution
238:minus the change in
64:van der Waals forces
1237:Molar concentration
1207:Dilution (equation)
872:2012JChPh.136k4709M
749:2018JChPh.149p3305C
656:10.1021/ja00418a009
629:10.1021/ja00426a036
413:sufficiently deep.
201:dielectric constant
126:dynamic equilibrium
107:stability constants
103:coordination number
1471:Chemical processes
1277:Isotopic abundance
1242:Mass concentration
1116:Chemical solutions
1073:10.1021/ed080p1194
429:Saturated solution
197:dimethyl sulfoxide
168:
111:ion-exchange resin
105:, and the complex
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1067:(10): 1194–1196.
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911:(22): 6455–6460.
881:10.1063/1.3694280
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704:(34): 8195–8202.
623:(10): 2886–2894.
603:978-1-891389-31-3
550:978-0-08-037941-8
518:978-0-13-201304-8
480:(14): 4029–4034.
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266:Gibbs free energy
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539:(2nd ed.).
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583:
579:
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329:Born equation
325:
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317:
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295:donor numbers
291:
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130:precipitation
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48:
44:
40:
36:
28:
22:
1399:
1335:Raoult's law
1314:
1287:Ternary plot
1282:Mixing ratio
1064:
1060:
1028:
1024:
1019:(Chemistry).
991:
950:
943:
908:
904:
898:
863:
859:
849:
832:
800:(1): 75–83.
797:
793:
783:
740:
736:
726:
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697:
691:
674:
670:
664:
647:
643:
637:
620:
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610:
567:
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536:
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508:
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477:
473:
411:
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398:
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367:, including
345:
333:
326:
318:
314:
302:ionic radius
299:
274:
255:
248:
244:
232:Gibbs energy
229:
213:
209:
205:conductivity
193:acetonitrile
169:
153:
139:
115:
84:
68:
34:
33:
1440:Lyonium ion
1355:Miscibility
1340:Henry's law
905:J Phys Chem
449:Water model
373:hydrophobic
306:lanthanides
1460:Categories
1435:Amphiphile
1430:Lipophilic
1425:Hydrophile
1420:Hydrophobe
1297:Solubility
1192:Saturation
1162:Suspension
1011:(part B),
1003:(part A),
842:1118681509
677:(2): 225.
456:References
118:solubility
1466:Solutions
1445:Lyate ion
1400:Solvation
1315:Solvation
1257:Normality
913:CiteSeerX
574:solvation
348:hydration
310:actinides
99:complexed
51:molecules
43:dissolved
35:Solvation
21:salvation
1415:Polarity
1374:Category
1262:Molality
1124:Solution
1045:19806616
970:45008511
935:22594454
890:22443792
824:20021399
775:30384680
718:28816050
494:29611710
417:See also
403:in vacuo
399:in vacuo
286:positive
282:negative
236:enthalpy
185:methanol
172:polarity
170:Solvent
163:Nile red
95:solution
1365:Solvent
1167:Colloid
1157:Mixture
868:Bibcode
816:8566551
766:6217855
745:Bibcode
290:entropy
262:entropy
240:entropy
189:acetone
181:ethanol
122:kinetic
91:solvent
47:ionized
39:solvent
1043:
1015:
1007:
999:
968:
958:
933:
915:
888:
840:
822:
814:
773:
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716:
601:
547:
515:
492:
270:Kelvin
195:, and
85:By an
62:, and
1187:Alloy
820:S2CID
564:IUPAC
87:IUPAC
71:solid
41:with
1041:PMID
1013:ISBN
1005:ISBN
997:ISBN
966:OCLC
956:ISBN
931:PMID
886:PMID
838:ISBN
812:PMID
771:PMID
714:PMID
599:ISBN
545:ISBN
513:ISBN
490:PMID
327:The
308:and
280:. A
256:The
1069:doi
1033:doi
923:doi
909:116
876:doi
864:136
802:doi
761:PMC
753:doi
741:149
706:doi
702:121
679:doi
652:doi
625:doi
578:doi
576:".
482:doi
478:122
352:DNA
1462::
1065:80
1063:.
1059:.
1039:.
1029:15
1027:.
964:.
929:.
921:.
907:.
884:.
874:.
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858:.
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796:.
792:.
769:.
759:.
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712:.
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675:18
673:.
648:98
646:.
621:98
619:.
588:^
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488:.
476:.
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191:,
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1372:(
1108:e
1101:t
1094:v
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878::
870::
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708::
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681::
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627::
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580::
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521:.
496:.
484::
23:.
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