13

Sol ut i ons
I . T h e I d ea l Sol uti o n a n d C o l l i g a t i v e P r o p e rt i e s

1 3 .1 IONS

KI N D S

O F SO LU T

A solution i s a homogeneous mixture of chemical species dispersed on a molecular scale. By this definition, a solution is a single phase. A solution may be gaseous, liquid, or solid. inar! solutions are composed of two constituents, ternar! solutions three, "uaternar! four. The constituent present in th greatest amount is ordinarily called the solvent# while those constituents-one or more-present in relatively small amounts are called the solutes. The distinction between solvent and solute is an arbitrary one. If it is convenient, the constituent present in relatively small amount may be chosen as the solvent. e shall employ the words solvent and solute in the ordinary way, reali!ing that nothing funda mental distinguishes them. "xamples of #inds of solution are listed in Table 13.1. $as mixtures have been discussed in some detail in %hapter 1 1 . The discussion in this chapter and in %hapter 1$ is devoted to liquid solutions. &olid solutions are dealt with as they occur in connection with other topics.
Ta % l e 1 3 . 1

$aseous solutions 'iquid solutions &olid solutions $ases dissolved in solids 'iquids dissolved in solids &olids dissolved in solids

(ixtures of gases or vapors &olids, liquids, or gases, dissolved in liquids )! in palladium, *! in titanium (ercury in gold %opper in gold, !inc in copper +brasses,, alloys of many #inds

D e) i n i t i o n o) the Idea l Solution

&'(

1 3 .& ION

D + F I N I TI O N O F T , + I D + - L S O LU T

The ideal gas law is an important example of a li.iting law. As the pressure appro aches !ero, the behavior of any real gas approaches that of the ideal gas as a limit. Thus all real gases behave ideally at !ero pressure, and for practical purposes they are ideal at low finite pressures. -rom this generali!ation of experimental behavior, the ideal gas is defined as one that behaves ideally at any pressure. e arrive at a similar limiting law from observing the behavior of solutions. -or simplicity, we consider a solution composed of a volatile solvent and one or more in volatile solutes, and examine the equilibrium between the solution and the vapor. If a pure liquid is placed in a container that is initially evacuated, the liquid evaporates until the space above the liquid is filled with vapor. The temperature of the system is #ept constant. At equilibrium, the pressure established in the vapor is pO# the vapor pressure of the pure liquid +-ig. ./ . . a,. If an involatile material is dissolved in the liquid, the equilibrium vapor pressure p over the solution is observed to be less than over the pure liquid +-ig. . / . .b,. &ince the solute is involatile, the vapor consists of pure solvent. As more involatile material is added, the pressure in the vapor phase decreases. A schematic plot of the vapor pressure of the solvent against the mole fraction of the involatile solute in the solution, / & # is shown by the solid line in -ig. ./.0. At 0 & 1 1# P 1 pO 2 as 0 & increases, p decreases. The important feature of -ig. ./.0 is that the vapor pressure of the dilute solution 30 & near !ero, approaches the dashed line connecting pO and !ero . 2epending on the particular combina tion of solvent and solute, the experimental vapor-pressure curve at higher concentrations of solute may fall below the dashed line, as in -ig. ./.0, or above it, or even lie exactly on it. )owever, for all solutions the experimental curve is tangent to the dashed line at 0 & 1 1# and approaches the dashed line very closely as the solution becomes more and more dilute. The e quation of the ideal line +the dashed line, is p 1 pO 4 pO0 & 1 p3+. x & ,.
*

If x is the mole fraction of solvent in the solution, then x

0&

., and the equation

5apor T# p O

1*
3a6

pO

1
3%6
5a por p ress u re l o7er i n g % ! a n i n volat i l e solu te.

F i g u re 1 3 . 1

D e) i n i t i o n o) the Idea l Solution

p p

&'(

p5
6

6-

I-x

F i g u re 1 3 . & 5apo r press u re as a )un8tio n o) / 0 7

F i g u re 1 3 .3
) or th e s olvent .

9 ao u l)s l a 7

becomes

313.16

which is 9aoult:s la7. It states that the vapor pressure of the solvent over a solution is equal to the vapor pressure of the pure solvent multiplied by the mole fraction of the solvent in the solution. 8aoult 7 s law is another example of a limiting law. 8eal solutions follow 8aoult 7 s law more closely as the solution becomes more dilute. The ideal solution is defined as one that follows 8aoult 7 s law over the entire range of concentrations. The vapor pressure of the solvent over an ideal solution of an involatile solute is shown in -ig. 13.3. All real solutions behave ideally as the concentration of the solutes approaches !ero. -rom "q. 313.16 the vapor pressure lo7ering# p o * p# can be calculated 9

po po

p 1 p o /p o p 1 /;p o .
4

31

/6p O# 313.&6

The vapor pressure lowering is proportional to the mole fraction of the solute. If several solutes, &# 3# . . . , are present, then it is still true that p 1 /p o 2 but, in this case, 1 * / 1 0; < 03 < . . . and In a solution containing several involatile solutes, the vapor pressure lowering depends on the sum of the mole fractions of the various solutes. *ote particularly that it does not depend on the #inds of solutes present, except that they be involatile. The vapor presssure depends only on the relative numbers of solute molecules. In a gas mixture, the ratio of the partial pressure of the water vapor to the vapor pressure of pure water at the same temperature is called the relative hu.idit!. hen multiplied by 111# it is the per8ent relative hu.idit!. Thus 8.). 1

31 3.36

P po

and

:8.). 1

P 31116. Po

5ver an aqueous solution that obeys 8aoult 7 s law, the relative humidity is equal to the mole fraction of water in the solution.

1 3 .3

- N - L=T I C - L F O 9 > O F T , + C , + > I C - L P O T + N T i - L I N I D +- L L I ? U I D S O L U T IONS

As a generali!ation of the behavior of real solutions the ideal solution follows 8aoult 7 s law over the entire range of concentration. Ta#ing this definition of an ideal liquid solution and combining it with the general equilibrium condition leads to the analytical expression of the chemical potential of the solvent in an ideal solution. If the solution is in equilibrium with vapor, the requirement of the second law is that the chemical potential of the solvent have the same value in the solution as in the vapor, or +. / .;, flliq 1 flvap , where fll iq is the chemical potential of the solvent in the liquid phase, flvap the chemical potential of the solvent in the vapor. &ince the vapor is pure solvent under a pressure p, the expression for flvap is given by "q. +. 3.;<, = assuming that the vapor is an ideal gas flvap 1 flap < 9T In p. Then "q. +./.;, becomes flliq 1 fla p < 9 T In p. >sing 8aoult 7 s law, p 1 xp o , in this equation and expanding the logarithm, we obtain

9T In the p5 < 9T In x. ap < vapor, If pure solvent were in equilibrium flliq 1 flwith pressure would be p 5 = the equilibrium condition is 5 flf=q 1 flap < 9 T In p ,
where flf=q signifies the chemical potential of the pure liquid solvent. &ubtracting this equation from the preceding one, we obtain fl l iq - flf=q 1 9 T In x. In this equation, nothing pertaining to the vapor phase appears = omitting the subscript liq, the equation becomes + . / .?, fl 1 fl 5 < 9T In x. The significance of the symbols in "q. +./. ?, must be dearly understood 9 fl is the chemical potential of the solvent in the solution, fl 5 is the chemical potential of the pure liquid sol vent, a function of T and p, and x is the mole fraction of solvent in the solution. This equa tion is the result we suggested in &ection . . . ?, as a generali!ation from the form obtained for the fl of an ideal gas in a mixture.
1 3 .$ C , + > I C - L PO T+NT I-L O F T , + S O LUT+ I N I N-9= ID + -L S O L U T I O N 2 - P P L I C-TI O N O F T , + @ I S* D U , + > + ? U -T I ON

The $ibbs-2uhem equation can be used to calculate the chemical potential of the solute from that of the solvent in a binary ideal system. The $ibbs-2uhem equation, "q. + . . . @A,, for a binary system 3 T# p constant, is +./ .A, The symbols without subscripts in "q. +. / .A, refer to the solvent = those with the subscript

&

&A&

S o l ution s

refer to the solute. -rom "q. +. / .A,, dB. 0 1 - +nBn 0 , dB. = or, since nBn 0 1 xBx! , we have

2ifferentiating "q. +./.?, #eeping T and %8 TBx, dx, so that dB.0 becomes
4

p constant, we obtain for the solvent dB. 1

dB. 0 1 - 8 T dx -. C! )owever, x
4

C 0 1 ., so that dx 4 dx! 1

1# or dx 1 - dx 0 . Then dB.0 becomes

dx! dB. 0 1 8 T - . C0 Integrating, we have B.0 1 8 T In C 0

4

C#

+. / .<,

where C is the constant of integration = since T and p are #ept constant throughout this manip>lation, C can be a function of T and p and still be a constant for this integration. If the value of C 0 in the liquid is increased until it is unity, the liquid becomes pure li"uid solute, and B.0 must be B. , the chemical potential ofpure li"uid solute. &o ifx 0 1 ., B. 0 1 B. . >sing these values in "q. +./.<,, we find B. 1 C# and "q. +. / .<, becomes +. / . B. 0 1 B. 4 8 T In C 0 7 D, "quation +./ .D, relates the chemical potential of the solute to the mole fraction of the solute in the solute. This expression is analogous to "q. +./ .?,, and the symbols have corresponding significances. &ince the B. for the solute has the same form as the B. for the solvent, the solute behaves ideally. This implies that in the vapor over the solution the partial pressure of the solute is given by 8aoult 7 s law 9 p ! 1 x! p E +./ .@, If the solute is involatile, p is immeasurably small and "q. +./.@, cannot be proved experimentally = thus it has academic interest only.
1 3 .B TI+ S C O l U @ -T I5 + P9OP+9

&ince the second term in "q. + . / .?, is negative, the chemical potential of the solvent in solution is less than the chemical potential of the pure solvent by an amount - 8 T In x. &everal related properties of the solution have their origin in this lower value of the chemical potential. These properties are 9 +., the vapor pressure lowering, discussed in &ection . / .0 = +0, the free!ing-point depression = +/, the boiling-point elevation = and +;, the osmotic pressure. &ince these properties are all bound together through their common origin, they are called 8olligative properties +colligative 9 from 'atin 9 8o*# together, ligare# to bind,. All of these properties have a common characteristic 9 They do not depend on the nature of the solute present but only on the number of solute molecules relative to the total number of molecules present. The B. versus T diagram displays the free!ing-point depression and the boiling-point elevation clearly. In -ig. . / .;+a, the solid lines refer to the pure solvent. &ince the solute is

p
I I

I ffim

w
F i g u re 1 3 .$
Co l l i g a tive properties.

involatile, it does not appear in the gas phase, so the curve for the gas is the same as for the pure gas. If we assume that the solid contains only the solvent, then the curve for the solid is unchanged. )owever, because the liquid contains a solute, the F.l of the solvent is lowered at each temperature by an amount - 8T In /. The dashed curve in -ig. . / .;+a, is the curve for the solvent in an ideal solution. The diagram shows directly that the intersection points with the curves for the solid and the gas have shifted. The new intersection points are the free!ing point, T7.r , and the boiling point, T , of the solution. It is apparent that the boiling point of the solution is higher than that of the pure solvent +boiling-point elevation,, while the free!ing point of the solution is lower +free!ing-point depression,. -rom the figure it is obvious that the change in the free!ing point is greater than the change in the boiling point for a solution of the same concentration. The free!ing-point depression and boiling-point elevation can be illustrated on the ordinary phase diagram of the solvent, shown for water by the solid curves in -ig. . / . ;+b,. If an involatile material is added to the liquid solvent, then the vapor pressure is lowered at every temperature as, for example, from point a to point %. The vaporpressure curve for the solution is shown by the dotted line. The dashed line shows the new free!ing point as a function of pressure. At . atm pressure, the free!ing points and boiling points are given by the intersections of the solid and dashed lines with the hori!ontal line at . atm pressure. This diagram also shows that a given concentration of solute produces a greater effect on the free!ing point than on the boiling point. The free!ing point and boiling point of a solution depend on the equilibrium of the solvent in the solution with pure solid solvent or pure solvent vapor. The remaining possible equilibrium is that between solvent in solution and pure liquid solvent. This equilibrium can be established by increasing the pressure on the solution sufficiently to raisethe F.l of the solvent in solution to the value of the F.l of the pure solvent. The additional pressure on the solution that is required to establish the equality of the F.l of the solvent both in the solution and in the pure solvent is cal.ed the os.oti8 pressure of the solution.
1 3 .C T, + SSION F 9 ++D I N @ * P O IN T D+P9+

%onsider a solution that is in equilibrium with pure solid solvent. The equilibrium con dition requires that +. /. F.l+ T, p# /, 1 F.lso l id+ T, p6# .3,

&A$

S ol ut i on s E

where e T, p# is the chemical potential of the solvent in the solution, p6 is the chemical potential of the pure solid. &ince the solid is pure# does not depend on any composition variable. In "q. +./ .. 3,, T is the equilibrium temperature, the free!ing point of the solution = from the form of "q. +./. .3,, T is some function of pressure and the mole
a

Bl x,

Bl s o l i d

Bl s o l i i T

x, fraction of solvent in the solution. If the pressure is constant, then T is function only of x. If the solution is ideal, then Bl T, p# x, in the solution is given by "q. +./.?,, so that "q. +./. .3, becomes
e

8earrangement yields where is the chemical potential of the pure liquid,B l 5 + T,p6 - Blsol ii T, p6 1 Bis lo the $ molar $ibbs energy offusion ofthe pure solvent at the temperature T. "quation f u s $fu 6 +. /.. ., becomes +./. .0, ln x 1 .$f 8 T us To discover how T depends on x, we evaluate +o TBo x,p 2ifferentiating "q. +. / .. 0, with respect to x, p being constant, we obtain &ince
**

8T

+./. . . ,

cedure is now reversed and we write "q. +. /. . /, in differential form and integrate 9

aT p ox p >sing the $ibbs-)elmholt! equation, "q. +.3. ?;,, Ho+ $BT,Bo TIp 1 - l.)BT0, we obtain . )fus +. / .. /, 8 T 0 ox p7 In "q. )fus is the heat of fusion of the pure solvent at the temperature T. The pro +./. ./,,
8
4

The lower limit . corresponds to pure solvent having a free!ing point To . The upper 7 limit corresponds to a solution that has a free!ing point T. The first integral can be evaluated immediately = the second integration is possible if is #nown as a function of temperature. -or simplicity we assume that is a constant in the temperature range from To to T= then "q. +./. .;, becomes

x1

d F/ xx 1 F
1

To

d T. 8T

+./. .;,

) fu s ) fus In x 1 - .. +G
8

)fus

,.

To

+./. .

&A$

S ol ut i on s E

?, This equation can be solved for the free!ing point T, or rather more conveniently for .fT, . T . To In x - 8..)f us 7 +. /. . A,

which relates the free!ing point of an ideal solution to the free!ing point of the pure solvent, To , the heat of fusion of the solvent, and the mole fraction of the solvent in the solution,

x.

The relation between free!ing point and composition of a solution can be simplified considerably if the solution is dilute. e begin by expressing the free!ing-point depression * dT in terms of the total molality of the solutes present, .# where . 1 .; < . 3 < . . . . 'et n and > be the number of moles and molar mass of the solvent, respectively = then the mass of solvent is n>. Then .; 1 n;Gn> 2 . 3 1 n 3 Gn> 2 . . . = or n; 1 n>.; 2 n 3

n>. 3 2 . . . The mole fraction of the solvent is given by n n . . . n < n; < n 3 < n < n>3.; < . 3 < . . ., < >.
Ta#ing logarithms and differentiating, we obtain In x
1

+./. . <, - In +.

< >.6# and

+./. . D,

d In x
"quation + . /. . /, can be written

> d. < >.

; dT 1 9 T d In x .

8eplacing

+. / .. @, )us If the solution is very dilute in all solutes, then . approaches !ero and T approaches To # and "q. +./. .@, becomes
4 4

d In x by the value in "q. +./..D,, we obtain 9 T ; d. > . dT 1 Ll, +. < >.6 >9 TC 1
Ll,)us

a.

p. m 1 5

Jf .

+./ .03,

The subscript, . 1 3, designates the limiting of the derivative, and K is the free!ing 1 To * T# 1 * d T# point depression constant. The free!ing-point depression so for dilute solutions we have +. /.0., 1 K 7

+-o e f,
a.

p, m 1 5

ef

dfef

which integrates immediately, if . is small, to

> 1 3.3.D3.?0 #gBmol, To

K

The constant K depends only on the properties of the pure solvent. -or water, 1 0</..? J, and Ll,)us 1 A33@.? FBmol. Thus

ef f ..
1

+./ .00,

+3.3 .D3.?0 #gBmol, +D./ .;;. FBJ mol, +0</..? J, 0 A33@.? FBmol

. . D?@< J #gBmo .

"quation +./ .00, provides a simple relation between the free!ing-point depression and the molal concentration of solute in a dilute ideal solution, which is often used to determine the molar mass of a dissolv.ed solute. If H; #g of a solute of un#nown molar mass, > 0 , are dissolved in w #g of solvent, then the molality of solute is . 1 H 0 Bw> 0 7 >sing this value

&AC

S oluti on s

Ta % l e 1 3 . & F ree;i n g * p o i nt de pressi o n 8onsta nts

%ompound ater Acetic acid Ben!ene 2ioxane *aphthalene p-dichloroben!ene %amphor p -dibromoben!ene

(B+#9gBmol, 3.3 . D3 3.3A33 3.3<D. 3.3D D . 3..0D/ 3. .;<3 3. . ?00 3.0/?@

t JK LC
3 .A.A ?.;? . . .< D3. . ?0.< .<D.; DA

J IB+J #gBmol,

..DA /.?< ?.3< ;.< . A.@D <. . . /<.< .0.?

for

. in "q. 313.&&6 and solving for > & yields

>&
I

K) H& M +, H )

The measured values of +, : H & # and H# together with a #nowledge of K ofthe solvent, ) value of K : to determine isincreases clear thatthe for ease a given of .# of thethe larger the suffice & . It ) the greater will be +,> andvalue accuracy measurement of +,) )2 ) . This to consequently, it is desirable choose a solvent having a large value of K ) . By examining "q. 313.&16 we can decide what sorts of compounds will have large values of K . -irst of ) all, we replace I1,)us by To I1S)us 2 this reduces "q. 31 3 .&16 to 9> K * 313 .&36 ) To I1S)us :
4

which shows that K increases as the product > To increases. &ince To increases as ) > increases, K increases rapidly as the molar mass of the substance increases. The ) increase is not very uniform, simply because I1S)us may vary a good deal, particularly when > is very large. Table 13 .& illustrates the behavior of K ) with increasing > . Because of variations in the value of I1S)us # mar#ed exceptions occur = the general trend is apparent, however.
N 1 3 .' T= SO L U ILI

The equilibrium between solid solvent and solution was considered in &ection 13.C. The same equilibrium may be considered from a different point of view. The word 6 solvent 6 as we have seen is ambiguous. &uppose we consider the equilibrium between solute in solution and pure solid solute. In this condition the solution is saturated with respect to the solute. The equilibrium condition is that the Fl of the solute must be the same everywhere, that is 313.&$6 Fl&3 T# p# x 0 , Fl& 3so dl T# p6# where 0 & is the mole fraction of solute in the saturated solution, and therefore is the solu%ilit! of the solute expressed as a mole fraction. If the solution is ideal, then
I

Fl:&3 T# p6 < 9 T In 0 &

Fl& 3So d6 3 T#

p6#
where Fl:&3 T#

p6 is the chemical potential of the pure li"uid solute. The argument then

&AC

S oluti on s

To

F i g u re 1 3 . B

Id ea l so l u % i l it! versus

T.

proceeds in exactly the same way as for the free!ing-point depression = the symbols refer to the solute, however. The equation corresponding to "q. +./. . ?, is In 0 &
I

+./.0?,
I

il,)us is the heat of fusion ofpure solute, To the free!ing point ofpure solute. >sing il,)us To ilS)us in "q. + . / .0?,, we obtain
In 0 &
I

+.

+./ . 0A,

"ither "q. +. /.0?, or "q. +./.0A, is an expression of the ideal la7 o)solu%ilit!. According to this law, the solubility of a substance is the same in all solvents with which it forms an ideal solution. The solubility of a substance in an ideal solution depends on the properties of that substance only. 'ow melting point To and low heat offusion both favor enhanced solubility. -igure ./.? shows the variation of the solubility, x , as a function of temperature for two substances with the same entropy of fusion but different melting points. The use of "q. +./ .0?, can be illustrated by the solubi lity of naphthalene. The melting point is D3.3 K% = the heat offusion is .@ 3D3 FBmoG. >sing these data we find from "q. +./ .0?, that the ideal solubility x 3.0A; at 03 K%. The measured solubilities in various solvents are given in Table ././. The ideal law of solubility is frequently in error if the temperature of interest is far below the melting point of the solid, since the assumption that il,)us is independent of temperature is not a very good one in this circumstance. The law is never accurate for
I

Ta % l e 1 3 .3

&olvent %hloroben!ene Ben!ene Toluene %%l ; )exane

&olubility C! 3.0?A 3.0;. 3.00; 3.03? 3.3@3

&olvent Aniline *itroben!ene Acetone (ethyl alcohol Acetic acid

&olubility C0 3. ./3 3.0;/ 3. . D / 3.3. D3 3.3;?A

! per.ission )ro. F . ,. ,ilde%rand and 9 . L. S8ott# The Solu%ilit! o) Nonele8trol!tes# 3d ed . Ne7 =orO P 9einhold# 1 ( B1# p . & A3 .

&AA

S o l ution s

solutions of ionic materials in water, since the saturated solutions of these materials are far from being ideal and are far below their melting points. As the table of solubilities of naphthalene shows, hydrogen-bonded solvents are poor solvents for a substance that cannot form hydrogen bonds.
1 3 .A NT + L +5-T I O N O F T , + OI L I N @ POI

%onsider a solution that is in equilibrium with the vapor o f the pure solvent. The equilib rium condition is that

Fl3 T# p# x,
If the solution is ideal, and

1 Flvap3 T#

313.&'6

p6. FlO3 T# p6
<

8 T In x

1 Flvap3 T#

p6#
Flvap * Fl O3 T# . In x -L

p6

8T The molar $ibbs energy of vapori!ation is

Ll@vap
so that

1 Flvap3 T# p6 * FlO3 T# p6#

L Ll@vap . In x 8T

313.&A6

*ote that "q. 313.&A6 has the same functional form as "q. 313. 1&6 except that the sign is changed on the right-hand side. The algebra which follows is identical to that used for the derivation of the formulas for the free!ing-point depression except that the sign is reversed in each term that contains either Ll@ or Ll,. This difference in sign simply means that while the free!ing point is depressed, the boiling point is elevated. e can write the final equations directly. The analogues of "qs. 313. 1 B6 and 313.1C6 are In x

vap +G L , 1 Ll, T To : 8
or

1
*

1 1 To 8 In x
<
* .

313.&(6

**

Ll,vap

The boiling point'of the solution is expressed in terms of the heat of vapori!ation and the boiling point of the pure solvent, Ll,vap and To # and the mole fraction x of solvent in the solution. If the solution is dilute in all solutes, then . approaches !ero and T approaches To . The boiling-point elevation constant is defined by 8 T? . 1> Ll,va p The boiling-point elevation, +,b 1 T * To # so that d+,b 1 d T. &o 313 .316 integrates to Jb

o.

3 13.316 . is small, "q. 313.316

II. $

p, m 1 5

&AA

S o l ution s

-or water, Jb 1.B

> 1.11A11B& #gBmol, To 3'3. 1B K# and il,vap $1 CBC FBmol, then 1&(( K #gBmol. The relation, "q. 31 3.3 16# between boiling-point elevation and
the

%ompound

Ta % l e 1 3 . $ o i l i n g *p oi n t e l evat i o n 8on sta nts

(B+#gBmol, 3.3.D3 3.3/03 3.3;A . 3.3? D . 3.3A33 3.3<D. 3.3D;0 3. .3@3

tb=a%

JbB+J #gBmol, 3. ? . 3.DA . .0/ . .<. /.3< 0.?/ 0.<@ 0.@/

ater (ethyl alcohol "thyl alcohol Acetone Acetic acid Ben!ene %yclohexane "thyl bromide

.33 A;.< <D.? ?A. . . . D./ D3.0 D . .; /D./

molality of a dilute ideal solution corresponds to that between free!ing-point depression and molality = for any liquid, the constant Jb is smaller than JF : The elevation of the boiling point is used to determine the molecular weight of a solute in the same way as is the free!ing-point depression. It is desirable to use a solvent that has a large value of Jb . In "q. +././3, if BM,.)vap is replaced by To '.&vap then Jb 1 8(To .
'.&vap

But many liquids follow Trouton7s 1 rule 9 '.&vap @3 FNJ mol. &ince 8 1 A.3 FNJ mol, Jb .3 larger approximately, then, the ( To . The higher the molar mass of the solvent, the value of Jb . The data in Table ./.; illustrate the relationship. &ince the boiling point To is a function of pressure, Jb is a function of pressure. The effect is rather small but must be ta#en into account in precise measurements. The %lausius %lapeyron equation yields the connection between To and p, which is needed to calculate the magnitude of the effect.
*

1 3 .( SU9+

O S > O TI C

P9+ S

The phenomenon of osmotic pressure is illustrated by the apparatus shown in -ig. . / .A. A collodion bag is tied to a rubber stopper through which a piece of glass capillary tubing is inserted. The bag is filled with a dilute solution of sugar in water and immersed in a bea#er
@lass tu%e

-r
,*P < '1

F i g u re 1 3 . C S i . p l e os.oti8 pressu re e/per i . en t.

&(1

S o l ution s

ofpure water. The level of the sugar solution in the tube is observed to rise until it reaches a definite height, which depends on the concentration ofthe solution. The hydrostatic pressure resulting from the difference in levels of the sugar solution in the tube and the surface of the pure water is the os.oti8 pressure of the solution. 5bservation shows that no sugar has escaped through the membrane into the pure water in the bea#er. The increase in volume of the solution that caused it to rise in the tube is a result of the passage of water through the membrane into the bag. The collodion functions as a se.iper.ea%le membrane, which allows water to pass freely through it but does not allow sugar to pass. hen the system reaches equilibrium, the sugar solution at any depth below the level of the pure water is under an excess hydrostatic pressure due to the extra height of the sugar solution in the tubing. The problem is to derive the relation between this pressure difference and the concentration of the solution.
1 3 .(.1 u at i o n T h e va n : t , o )) + "

The equilibrium requirement is that the chemical potential of the water must have the same value on each side of the membrane at every depth in the bea#er. This equality of the chemical potential is achieved by a pressure difference on the two sides of the membrane. %onsider the situation at the depth h in -ig. 13.C. At this depth the solvent is under a pressure p# while the solution is under a pressure p < n . If pe T# p < n# x, is the chemical potential of the solvent in the solution under the pressure p < n# and poe T# p6 that of the pure solvent under the pressure p# then the equilibrium condition is pe T# p < n# x, 1 poe T# p6# 313.3&6 and

313.336
The problem is to express the p of the solvent under a pressure p < n in terms of the p solvent under a pressure p. -rom the fundamental equation at constant T# we have dpo 1 .<K dp. Integrating, we have

313.3$6
This reduces "q.

313.336 to

f4.t 5O dp

<

8T In x 1 O.

313.3B6

In "q. 313.3B6# .<K is the molar volume of the pure solvent. If the solvent is incompressible, then !o is independent of pressure and can be removed from the integral. Then =On < 8 T ln x 1 1# 313.3C6 which is the relation between the osmotic pressure n and the mole fraction of solvent in the solution. Two assumptions are involved in "q. 313.3C6 2 the solution is ideal and the solvent is incompressible. In terms of the solute concentration, In x 1 In 31 * 0; , . If the solution is dilute, then 0; 1 2 the logarithm may be expanded in series. Jeeping only the first term, we obtain In 31

* x ;, 1

since n!

n in the dilute solution. Then "q. 313

n 1

.3C6 becomes 313 .3'6

n! 8 T . n O5

By the addition rule the volume of the ideal solution is O 1 n O 5 < n! O . If the solution is dilute, n! is very small, so that O n This result reduces "q. 313.3'6 to
n 1
* *

n! 8 T O

!o.

or

n 1

c8 T.

313.3A6

In "q. 313.3A6# c 1 n!B O, the concentration of solute +molBm / , in the solution. "quation 31 3.3A6 is the van7t )off equation for osmotic pressure. The stri#ing formal analogy between the van7t )off equation and the ideal gas law should not go unnoticed. In the van7t )off equation, n ! is the number of moles of solute. The solute molecules dispersed in the solvent are analogous to the gas molecules dispersed in empty space. The solvent is analogous to the empty space between the gas molecules. In the experiment shown in -ig. 13.'# the membrane is attached to a movable piston. As the solvent diffuses through the membrane, the piston is pushed to the right = this continues until the piston is flush against the right-hand wall. The observed effect is the same as ifthe solution exerted a pressure against the membrane to push it to the right. The situation is comparable to the free expansion of a gas into vacuum. Ifthe volume of the solution doubles in this experiment, the dilution will reduce the final osmotic pressure by half, Nust as the pressure of a gas is halved by doubling its volume. In spite of the analogy, it is deceptive to consider the osmotic pressure as a sort of pressure that is somehow exerted by the solute. 5smosis, the passage of solvent through the membrane, is due to the inequality of the chemical potential on the two sides of the membrane. The #ind of membrane does not matter, but it must be permeable only to the solvent. *or does the nature of the solute matter = it is necessary only that the solvent contain dissolved foreign matter which is not passed by the membrane. The mechanism by which the solvent permeates the membrane may be different for each different #ind of membrane. A membrane could conceivably be li#e a sieve that allows small molecules such as water to pass through the pores while it bloc#s larger molecules. Another membrane might dissolve the solvent and so be permeated by it, while the solute is not soluble in the membrane. The mechanism by which a solvent passes through a membrane must be examined for every membrane-solvent pair using the methods of chemical #inetics. Thermodynamics cannot provide an answer, because the equilibrium result is the same for all membranes.

Se.iper.ea%le .e.%rane
. . . . . . . . . . . . . . . . . .

Solution P 3gas6

* Piston

Pure solvent 3va8uu.6

F i g u re 1 3 . ' Os.oti 8 a n a )og o) the F o u l e e/per i .ent .

&(&

S oluti on s

1 3 .(.& e

> ea s u r e . e n t o ) O s . ot i 8 P r ess u r

The measurement of osmotic pressure is useful for determining the molar masses of materials that are only slightly soluble in the solvent, or which have very high molar masses +for example, proteins, polymers of various types, colloids,. These are convenient measure ments because of the large magnitude of the osmotic pressure. At 0? K%, the product 9T 99999990;D3 FBmoG. Thus, for a . molN' solution 38 1 .333 molNm / ,, we have A n 1 89 T 1 0.;D C .3 Pa 1 0;. ? atm. This pressure corresponds to a height of a column of water of the order of D33 ft9 &imply to #eep the experiment in the laboratory, the solutions must be less than 3.3 . molar, and are preferably of the order of 3.33. molar. This assumes that we are using an apparatus of the type shown in -ig. ./.A. Oery precise measurements of osmotic pressures up to several hundred atmospheres have been made by ). *. (orse and F. %. . -ra!er, and by 'ord Ber#eley and ". $. F. )artley using special apparatus of different design. In a molar mass determination, if H & is the mass of solute dissolved in the volume, 5# then n 1 7 & 9 TI> & 5# or

"ven when H & is small and > & large, the value of n is measurable and can be translated into a value of >& M 5smosis plays a significant role in the function of organisms. A cell that is immersed in pure water undergoes plasmolysis. The cell wall permits water to flow into it = thereupon the cell becomes distended, the wall stretches until it ultimately ruptures or becomes lea#y enough to allow the solutes in the cellular material to escape from the interior. 5n the other hand, if the cell is immersed in a concentrated solution of salt, the water from the cell flows into the more concentrated salt solution and the cell shrin#s. A salt solution which is Nust concentrated enough so that the cell neither shrin#s nor is distended is called an isotoni8 solution. 5smosis might be called the principle of the prune. The s#in of the prune acts as a membrane permeable to water. The sugars in the prune are the solutes. ater diffuses through the s#in and the fruit swells until the s#in ruptures or becomes lea#y. 5nly rarely are plant and animal membranes strictly semipermeable. -requently, their function in the organism requires that they pass other materials, as well as water. (edicinally, the osmotic effect is utili!ed in, for example, the prescription of a salt-free diet in some cases of ab normally high fluid retention by the body.
? U +ST I O N S 13.1 Is the lowering of the chemical potential of a solvent in an ideal solution, "q. +./.?,, an

enthalpy effect or an entropy effect Q "xplain. 13.& Interpret +a, free!ing-point depression and +b, boiling point elevation in terms of )l as a measure of 6 escaping tendency.6 13.3 )ow does the temperature dependence of the solubility of a solid in a liquid illustrate 'e%hatelier7s principle Q

13.$ 9everse osmosis has been suggested as a means of purifying sea water +roughly an *a%l-)! 5

&(&

S oluti on s

solution,. )ow could this be accomplished with an appropriate membrane, with special attention placed on the required pressure on the solution Q

&(&

S oluti on s

P9O
13 . 1

L+>S

13.&

Twenty grams of a solute are added to .33 g of water at 0? 3c. The vapor pressure of pure water is 0/.<A mm)g = the vapor pressure of the solution is 00.;. mm)g. a, %alculate the molar mass of the solute. b, hat mass of this solute is required in .33 g of water to reduce the vapor pressure to one half the value for pure water Q )ow many grams of sucrose, % . 0 ) 00 3 > , must be dissolved in @3 g of water to produce a solu tion over which the relative humidity is D3 :Q Assume the solution is ideal. &uppose that a series of solutions is prepared using .D3 g of ) 0 3 as a solvent and .3 g of an involatile solute. hat will be the relative vapor pressure lowering if the molar mass of the solute is 9 .33 gBmol, 033 gBmol, .3,333 gBmol Q a, -or an ideal solution plot the value of pGpo as a function of C 0 , the mole fraction of the solute. b, &#etch the plot of pGpo as a function of the molality of the solute, if water is the solvent. c, &uppose the solvent +for example, toluene, has a higher molar mass. )ow does this affect the plot of pGpo versus mQ )ow does it affect pGpo versus C 0 Q d, "valuate the derivative of 3p o * p,Bpo with respect to m, as m --4 5. A stream of air is bubbled slowly through liquid ben!ene in a flas# at 03.3 K% against an ambient pressure of .33. ?A #Pa. After the passage of ;.D3 ' of air, measured at 03.3 K% and .33.?A #Pa before it contains ben!ene vapor, it is found that ..<3? g of ben!ene have been evaporated. Assuming that the air is saturated with ben!ene vapor when it leaves the flas#, calculate the equilibrium vapor pressure of the ben!ene at 03.3 3c. Two grams ofben!oic acid dissolved in 0? g of ben!ene, Jf ;.@3 J #gBmol, produce a free!ing point depression of . . A0 J. %alculate the molar mass. %ompare this with the molar mass obtained from the formula for ben!oic acid, % A ) s %55). The heat of fusion of acetic acid is . . .<0 #FBmol at the melting point .A.A. 3c. %alculate Jf for acetic acid. The heat of fusion of water at the free!ing point is A33@.? FBmol. %alculate the free!ing point of water in solutions having a mole fraction of water equal to 9 . .3, 3.D, 3.A, 3.;, 3.0. Plot the values of T versus x. "thylene glycol, % 0 )i5)h , is commonly used as a permanent antifree!e = assume that the mixture with water is ideal. Plot the free!ing point of the mixture as a function of the volume percent of glycol in the mixture for 3 : , 03 : , ;3 : , A3 :, D3 :. The densities are 9 ) 0 3, ..33 gBcm / , glycol, .... gBcm / R )fus +) 0 3, 1 A33@.? FBmol.
JJ

13.3

13.$

13.B

13.C

13.'

13.A

13. (

13 . 1 1

13. 1 1

Assume that )fus is independent of the temperature and that the thermometer available can measure a free!ing-point depression to an accuracy of R 3.3. J. The simple law for free!ing point depression, 5f 1 J rm, is based on the limiting condition that m 1 5. At what molality will this approximation no longer predict the result within the experimental error in water Q If the heat of fusion depends on temperature through the expression )fus 1 )o 4 %p+ T To,,

where %p is constant, then the value of 5f can be expressed in the form 5f 1 am 4 bm 0 4 . . . , where a and b are constants. %alculate the values of a and b. H)int9 This is a Taylor series, so evaluate +"P5BDm 0 , at m 1 3.I
1 3. 1 &

-or %%I; , Jb 1 ?.3/ J #gBmol and J r 1 / . . D J #gBmol. If /.33 g of a substance in .33 g %%l ; raises the boiling point by 3.A3 J, calculate the free!ing-point depression, the relative vapor pressure lowering, the osmotic pressure at 0? K%, and the molar mass of the substance. The density of %%l; is . . ?@ gBcm / and the molar mass is . ? /.D0/ gBmol.

P ro %l e. s

&(3

13.13 %alculate the boiling-point elevation constant for each of the following substances.

Su%stan8e

t%t8
?A. . D3.0 A.. ? - . ?@ <<.0

illivapB3FBg,
?03.@ /@;.A 0;< ?<< ;0A.D

Acetone, +%) / h%5 Ben!ene, % A ) A %hloroform, %)%l / (ethane, %); "thyl acetate, %) / %3 0 % 0 ) ? the values of K % versus the product ( Tb .

the boiling point of the liquid depends on the pressure, K % is a function of pressure. the value of K % for water at <?3 mm)g and at <;3 mm)g pressure. >se the data in the text. Assume illivap is constant. 13.1B a, -or p-dibromoben!ene, % A ) ; Br 0 , the heat of fusion is D?.D Fig = the melting point is DA K%. %alculate the ideal solubility at 0? K%. b, -or p-dichloroben!ene, % A ) ; %. 0 , the heat of fusion is .0;./ Fig = the melting point is ?0.< d8. %alculate the ideal solubility at 0? K%. 13.1C The melting point of iodine is . . /.A K% and the heat of fusion is .?.A; #FBmol. a, hat is the ideal solubility of iodine at 0? K% Q b, )ow many grams of iodine dissolve in .33 g hexane at 0? K% Q 13.1' In .33.3 g ben!ene, <3. D? g naphthalene, % l 5 )s , dissolve at 0? K% and .3/.AA g dissolve at /? K%. Assume the solution is ideal. %alculate il)lius and T. for naphthalene.
13.1A If A.33 g of urea, +*) 0 h%5, is dissolved in . .33 ' of solution, calculate the osmotic

pressure the solution at 0< K%. a vertical tube with a cross-sectional area of . .33 cm 0 R The bottom of the tube is with a semipermeable membrane and . .33 g of glucose, % A ) . 0 3 A , is placed in the tube. The closed end of the tube is immersed in pure water. hat will be the height of the liquid level in the tube at equilibrium Q The density of the solution may be ta#en as . .33 gBcm 0 = the sugar concentration is assumed to be uniform in the solution. hat is the osmotic pressure at equilibrium Q 3t 1 0?K % = assume a negligible depth of immersion., osmotic of ;33 Pa. hat is the molar ass of the ubtance Q . The complete 8 n 15 ex pressi5n &m for osmotIc pressure I& gIven by "q. +. / . /A,. ce 1 & and 5 1 n5o 4 n 0 51 # where 5O and 51 are constants, the mole numbers n and n 0 can be ex pressed in terms of 5# !o# 5& # and 8. %ompute the value of 4 in these terms. Then evaluate 3Ar8lA8h ;at 8 1 3 and show that it is to 9 T. & 4 5:C6# where 5: 1 5& - t va. b, By evaluating 3A r8lA8 h at 8 1 3, show that r8 *ote that this is equivalent to writing a modified van der aals equation, r8 1 n &9 TI3 5 n ; 5:6# and expanding it in a power series.
4 .

13.&1 At 0? K% a solution containing 0.?3 g of a substance in 0?3.3 cm / of solution exerts an

.-