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Theory of Dilute Solution
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Colligative Properties
Dilute solution containing non-volatile
solutes exhibit the following properties1.Lowering of the vapour pressure
2.Evevation of the boiling point
3.Depression of the freezing point
.!s"otic pressure
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Lowering of vapour pressure# $%!&L'()(
L%*
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Lowering of vapour pressure#
$%!&L'()( L%*
P % + X %P °%
where
, X % is the "ole fraction of co"poun %
, P °% is the nor"al vapor pressure of % at that te"perature
NOTE: 'his is one of those ti"es when ou want to "a/e sure ou have the
vapor pressure of the solvent.
0ole raction X
moles of A
total moles in solution X
A =
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Positive deviations from Raoult's
Law
%ssu"e that we have two
particel4 % an 5 are "ixe
%ttraction of particel % an %are greater than % an 5
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negative deviations from Raoult's
Law
%ttraction of particel % an 5
are greater than % an %
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0easure"ent of lowering of vapour
pressure
1. baro"etric "etho
2. "ano"etric "etho
3. !swal an *al/ers na"ic
"etho
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5aro"eter "etho
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0ano"eter "etho
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!swal an *al/ers na"ic
"etho
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5oiling pointelevation
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*hen a li6ui is heate4 its vapour
pressure rises an when it e6uals the
at"ospheric pressure the li6ui boils.'he aition of non-volatile solute
lowers the vapour pressure conse6uentl
elevates the boiling point as the solution
has to be heate a higher te"perature to"a/e its vapoure pressure beco"e e6ual
to at"ospheric pressure.
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Solutions
7f
'b boiling point of the solvent'boiling point of the solution
8'elevation of boiling point
so
8'+'-'b
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AB = AD
AC AE
T1 = P-P1
T1-Tb P-P2
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Deter"ination of "olecular
"ass fro" elevation ofboiling point(ince P is constant for the sa"e solvent at afixe te"perature4 fro" 1 we can write
8'+ P-P1 P
5ut fro" $aoult)s law for ilute solution
P-P19 w0
P *"(ince 0"ol "ass of solvent is constant
P-P19 w
P *"
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Solutions
8'9 w x 1
" *8'+ :b x w x 1
" *
:b constant
:b+8' x :g-solvent
"ol solute
:b + $'b2
1;;; x Ltherefore :b+ ;.<2 :=:g
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0easure"ent of boiling point
elevation1. Lanssberger-*al/er-0etho
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2. Cottrel)s 0etho
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0olecular view of $aoult)s law#
reezing point epression
Depens on the solute onl being in the li6ui phase ewer water "olecules at surface# rate of freezing rops
7ce turns into li6ui
Lower te"perature to regain balance
Depression of freezing point
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Solutions
!s"otic pressure
(olvent passes into "ore concsolution increasing its volu"e
'he passage of the solvent canbe prevente b application ofa pressure
'he pressure to preventtransport is the osmotic pressure
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Calculating os"otic pressure
'he ieal gas law states
5ut n=> + 0 an so
*here 0 is the "olar concentration of
particles an Π is the os"oticpressure
?ote# molarity is use not molality
nRT PV =
MRT =Π
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!s"otic pressure an
"olecular "ass0olar "ass can be co"pute
fro" an of the colligative
properties
!s"otic pressure provies the
"ost accurate eter"ination
because of the "agnitue of Π ;.;2;; 0 solution of glucose exerts an os"otic pressure of
[email protected] "" Ag but a freezing point epression of onl ;.;2BC
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Solutions
Beckmann’s method
• % ver sensitive ther"o"eter4 calle a Be!mannt"ermometer is use4 which has a large bulb an onl sixegrees on the whole scale
• (olvent are weighe into the tube %
• 'he tube % is fitte through a cor/ into a large test-tube 54which serves as an air-ac/et
• 'he tube 5 is supporte in a freezing "ixture containe inthe large ar C
• 'he "ercur falls steail to a certain point4 when thesolvent is slightl supercoole. reezing then co""ences4the te"perature at once runs up to the freezing point4 anafterwars re"ains stationar
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Rast’s Camphor method
• % /nown weight of ca"phor is ta/en an powere finel
• 'o this a /nown weight of soli solute is ae
•
'he "ixture is "elte to for" a ho"ogeneous solution4 coole4 anpowere r
• 'he "ixture is ta/en in a capillar tube whose one en is seale
•
7ts "elting point is eter"ine carefull b the conventional "elting pointeter"ination "etho
• 'he "elting point of the pure sa"ple of ca"phor is eter"ine separatelusing another capillar tube. 'he ifference in the "elting points gives 8'f
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%pplication of 5ec/"ann
$ast Cha"por 0etho
" + 0olecular weight of solute
∆T + reezing=0elting point epression
K f + Constantsw + *eight of solute
* + *eight of solvent
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Solutions
Colligative Properties of
Electroltes The colligative properties of solution depend
solely on the total number of solute particlespresent in solution. The various electrolytes
ionize and yield more than one particle performula unit in solutin. Therefore the colligativeeect of an electrolyte solution is always greaterthan that of nonelectrolyte of the same molalconcentration.
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!an’t "o #actor
!an’t "o #actor $i% is de&ned as the
ratio of the colligative eect producedby an electrolyte solution to thecorresponding eect for the sameconcentration of nonelectrolytesolution.
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$elation between >an)t Aoff
actor an Degree of Dissociation
'uppose ( mole of an electrolyte iscapable of forming n ions on completedissociation. )nd α is degree ofdissociation* then +
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Solutions
,umber of undissociatedmoleculs - (α
,umber of ions produced - α n
Total number of particles - (α α n
"ence*
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)ctivity Coe/cient0., 1ewis discovered that the
e2perimentally determined value ofconcentration whether of moleculesor ions in solution is less than theactual concentration. The apparent
value of concentration is termedactivity* de&ned as the ratio betweenthe activity and actual concentrationof the molecul or ion in solution