Chapter 11 PROPERTIES OF SOLUTIONS

Solution:
Solution is a homogeneous mixture
consists of solvent and solute(s); aqueous solution has water as solvent;
concentrated solution - contains a high amount of dissolved solute(s);
dilute solution contains low amount of dissolved solute(s);
saturated solution contains the maximum amount of dissolved solute(s) that is
normally possible at a particular temperature;
supersaturated solution contains more dissolved solute(s) than it normally does to
give saturated solutions at a particular temperature.

Types of Solutions

State of State of State of

Solvent Solute Solution !xamples

"as "as "as #ir$ natural gas

%iquid %iquid %iquid #lcoholic beverages$
#ntifree&e solution;
%iquid solid liquid seawater$ sugar solution
%iquid gas liquid carbonated water (soda)
#mmonia solution;
Solid solid solid metal alloys' brass$ bron&e$..
Solid gas solid hydrogen in platinum

Solubility and Equilibrium in Solution

(he solubility of a substance is the amount of solute (in grams) that is dissolved in a
given quantity of solvent to give a saturated solution at a particular temperature.
# saturated solution is one that contains the maximum quantity of dissolved solute that is
normally possible at a given temperature$ where a state of dynamic equilibrium exist between
dissolution and crystalli&ation.
Solubility is temperature dependent. )or example$ the solubility of *+,- is about -.. g per /..
g water at 0.
o
1 and 2- g per /.. g water at 3.
o
1. 4hen a solution that is almost saturated
at a higher temperature is cooled to a lower temperature where the solubility is lower$ the
excess solute would normally precipitate out to give a saturated solution at the lower
temperature. 5owever$ if the solution is cooled down too rapidly and the solute fails to seed$
precipitates will not form and the resulting solution would contain more dissolved solute than it
would be in a normal saturated solution. (he resulting solution is said to be supersaturated.
# supersaturated solution is one that contains more dissolved solute than it normally
possible under normal condition. (he solution is unstable and crystalli&ation will occur readily
by seeding (introducing particles that provide nuclei for precipitation).
1
Fractional Crystallization (Re-crystallization)
Since the solubility of most compounds generally increases at higher temperatures$ re-
crystalli&ation can be carried out in the purification of certain compounds. # good recovery
can be obtained from re-crystalli&ation if the substance has a very high solubility at higher
temperature$ but very low solubility at low temperature. )or example$ *+,- has a solubility of
about 2- g per /.. g 50, at 3.
o
1$ and /6 g per /.. g 50, at .
o
1. 7f a saturated solution of
*+,- at 3.
o
1 is cooled to ,
o
1$ 36 g of solid *+,- will crystalli&e out.
!xercise-/'
/. (he solubility of +531l in water is 08 g9/.. g 50, at .
o
1 and 68 g9/.. g 50, at 26
o
1. (a)
7f :6 g of +531l is dissolved in /6. g of water at 26
o
1$ would you get is a saturated or
unsaturated solution; (b) 4hen this solution is cooled to .
o
1$ how many grams of the
+531l will precipitate out$ assuming supersaturation does not occur;

11.1 Solution Composition

1oncentration' how much solute is in a solution;
Units of Concentration:
/. <ass =ercent$ > (w9w) ? <ass of solute x /..>
<ass of solution
0. @olume =ercent > (v9v) ? @olume of Solute x /..>
@olume of Solution
-. <olarity (M) ? +o. of moles of solute
%iters of solution
3. Molality (m) ? +o. of moles of solute
*g of solvent
6. +ormality (N) ? +o. of equivalent of solute
%iter of solution
2. <ole fraction$ Xi ? <ole of a component
(otal moles of components in solution

!xercise-0
/. # solution is prepared by dissolving 0.0A6 g of +a,5 in enough water to maBe a 0....
m% solution. 1alculate the molarity of the solution.
0. 1alculate the mass percent of the solute in a solution containing /:.6 g +531l in 386 g of
water. 4hat is the molality of the solution;
-. 5ow many grams of +a1l must be dissolved in /... g of water to maBe a solution of -.32
m in +a1l;
3. # solution is prepared by mixing /2.. g of 15-,5 and 6... g of water. (a) 4hat is the
mass percent of methanol in the solution; (b) what is the mole fraction of each
component in the solution; (c) 7f the density of solution is ..:66 g9m%$ what is the
molarity and molality of 15-,5$ respectively$ in the solution;

2
11.2 The Energ o! Solution Formation
Solution rocesses:
Steps involved in the formation of solution
/. pure solute separated solute particles; H/ C .; (endothermic process)
0. pure solvent separated solvent molecules; H0 C .; (endothermic process)
-. separated solvent and solute molecules solution; H- D .; (exothermic process)

+et' pure solute E pure solution solution; Hsoln ? H/ E H0 E H- ;

!+!F"G is needed to breaB intermolecular forces in solvent and solute in order to

separate the molecules9ions apart. 4hen molecules mix to form solution$ there is an increase
in intermolecular interaction and energy is released.

The Energ Terms !or "arious Tpes o! Solutes an# Sol$ents

H/ H0 H- Hsoln ,utcome

=olar solvent$ %arge %arge %arge$ Small Solution forms

polar solute negative
=olar solvent$ Small %arge Small %arge$ Solution does
nonpolar solute positive not form
+onpolar solvent$ Small Small Small Small Solution forms
nonpolar solute
+onpolar solvent$ %arge Small Small %arge$ Solution does
polar solute positive not form

Types of Sol!ent-Solute "nteractions

%ondon dispersion forces;
=ermanent dipole-dipole attractions;
=ermanent dipole-induced dipole attractions;
7on-dipole attractions;
7on-induced dipole;
5ydrogen bonding.
Solution Formation of "onic Compounds
<any ionic compounds dissolve in water but not in organic or nonpolar solvents. 4ater
molecules are very polar and interact strongly with the ionic species (cations and anions)
through ion-dipole interactions. Such interactions results in negative enthalpies$ called the
solvation or hydration energy. (he overall solution process may be exothermic or endothermic$
depending on which enthalpy is larger.
3
1onsider the dissolution process to form +a1l solution'
/. Hissociation of +a1l into gaseous ions'
+a1l(s) +a
E
(g) E 1l
-
(g); H/ ? A82 BI9mol
0. 5ydration of +a
E
ions' +a
E
(g) E n50, +a
E
(aq); 50 ? -833 BI9mol
-. 5ydration of 1l
-
ions' 1l
-
(g) E n50, 1l
-
(aq); 5- ? 2/ BI9mol

+et' +a1l(s) +a
E
(aq) E 1l
-
(aq); Hsoln ? H/ E H0 E H- ? - BI9mol

(he formation of +a1l solution is slightly endothermic. Jut why would an endothermic process
be spontaneous; (he main driving force in solution formation is the state of higher disorder$
that is the state higher entropy in solution compared to the original solid +a1l.
# solution that is formed with Hsoln ? . is called an ideal solution. (hose formed with
positive or negative Hsoln are nonideal solutions. 4hether a solute will dissolve or not in a
particular solvent$ or whether the solution formed is ideal or nonideal$ depends on the
intermolecular interactions between solute and solvent particles.
##$% Factors &ffectin' Solubility
Structural Effects
(here is a correlation between molecular structure and solubility. # solution will form if
both solute and solvent have similar molecular structures$ polarity and types of interactions
Klike dissolves likeL. )or example$ nonpolar substances liBe grease and oil are soluble in
nonpolar organic solvent such as hexane (125/3) and gasoline (185/8). 7onic and polar
compounds such as salts$ mineral acids$ and sugar are soluble in polar solvents such as water
and methanol.
Effect of Temperature:
(he solubility of solids generally increases as temperature increases$ which implies that
dissolving solid substances is generally an endothermic process (Hsoln C .). (he %e 1hatelierMs
principle states that an endothermic process favors high temperature. (he solubility of some
ionic compounds that contain S,-
0-
$ S,3
0-
$ Se,3
0-
$ #s,3
--
and =,3
--
$ are found to decrease as
the temperature increases. (hese compounds have negative enthalpy of solution (Hsoln D .).
)or gases dissolving in liquid solvents$ their solubility decreases as the temperature
increases; the dissolution of gaseous solutes is an exothermic process - when a gas dissolves
heat is given off. "ases are more soluble at low temperature than at high temperature. (his
temperature effect on the solubility of gaseous substances has important environmental
implications as a result of the widespread uses of water from laBes and rivers in the industrial
cooling system. (he discharged water from the cooling system bacB into the laBes or rivers is
significantly warmer than the natural ambient temperature$ which causes t(ermal pollution.
(he rise in ambient temperature of laBe or river water lowers the concentration of dissolved
oxygen$ which can be detrimental to the survival of aquatic lives.
Effect of ressure:
4
=ressure has little effect on the solubility of solids or liquids$ but significantly increases
the solubility of gases. #ccording to )enry*s +a,$ the solubility of gases is directly
proportional to the partial pressure of the gas above the solution' C % -$ where 1 ?
concentration of gas in solution$ = ? gas pressure above the solution$ and k ? 5enryNs
constant characteristic of the gas and solvent. (he solubility of gases is normally expressed in
m% of gas at S(= per liter of solvent.
5enryNs law is obeyed most accurately for a very dilute solutions of gases that do not
dissociate or react with the solvent. )or example$ 5enryNs law is obeyed by oxygen and
nitrogen gases dissolving in water$ but not by carbon dioxide or ammonia$ because the latter
gases react with water as follows'
1,0(g) E 50,(l) 501,-(aq) 5-,
E
(aq) E 51,-
-
(aq);
+5-(g) E 50,(l) +53
E
(aq) E ,5
-
(aq)
!xercise--'
/. (he solubility of 50S gas in water at 0.
o
1 and / atm pressure is 068 m% (measured at
S(=) per /.. g 50,. (a) 4hat is the mass percent of dissolved 50S; (b) 4hat is the
molality of the 50S solution; (c) 4hat is the solubility of 50S gas expressed in m% of 50S
(at S(=) per /.. g 50, when the temperature is 0.
o
1 and the partial pressure of the gas
is 066 torr;

"deal and .on-"deal Solutions

1onsider a binary solution consisting of components # O J; there exist interactions of
the types' # #$ # J$ and J J
Case #' 7nteractions' & ' ? & & ? ' '; 5 ? . and @ ? .
7n solutions composed of ben&ene(1252)-toluene(1A58)$ hexane(125/3)-heptane1A5/2)$
ethanol(1056,5)-methanol(15-,5)$ etc.$ intermolecular interactions between identical
molecules and those between non-identical molecules are relative of similar magnitude. Such
solutions tend to obey FaoultNs law and are called ideal solutions$ where =# ? X#=
o
#.
Case /' 7nteractions' & ' C & & P ' '; 5 D .$ @ D .;
4hen intermolecular interactions between non-identical molecules are stronger than
those between identical molecules$ the solution shows negative deviation from ideal behavior.
)or example$ in chloroform (151l-)-acetone (1-52,) mixture$ dipole-dipole interactions
between chloroform and acetone molecules are stronger than the chloroform-chloroform or
acetone-acetone interactions$ separately. (he vapor pressure of the solution tends to be lower
than that calculated for ideal solution based on the FaoultNs law (that is$ =# D X#P#)
1l
Q 15-
1l15
RRR..
,

1
Q 15-
1l
1hloroform #cetone
5
Case %' 7nteractions' & ' D & & P ' '; 5 C .$ @ C .
7n another type of solutions$ such as the acetone-carbon disulfide (1S0) mixture$
interactions between identical molecules are stronger than those between non-identical
molecules. # polar acetone interacts relatively strongly with another polar acetone than with a
nonpolar carbon disulfide molecule$ and vice versa. Such a solution shows a positive deviation
from ideal behavior. (he vapor pressure of the solution tends to be higher than that predicted
from FaoultNs law for ideal solutions; (that is$ =# C X#=#)
15- 15- 15-
S

S
RRR.
S

S ,

1 +
RRR
,

1 S

S
RRR..
,

1
15- 15- 15-
(Hispersion force) (permanent dipole-dipole) (dipole-induced dipole)
Case 0' 7n extreme cases$ where the interactions are' & ' DD & & P ' '$
the components do not mix; instead they form two separate layers$ liBe water and oil.
(herefore$ there must be sufficiently strong interactions between solvent and solute particles
for two substances to form a solution. Solutions composed of the same type of components$
where interactions between identical and non-identical components in solutions are of
relatively similar magnitude$ tend to form ideal mixtures and obey FaoultNs law. 4hile those
solution in which the strength of interaction between identical and non-identical components
are very different$ they deviate from ideal behavior and do not obey FaoultNs law. 4hen
interactions between non-identical components are weaBer or stronger than those between
identical components$ the solutions tend to show deviation from FaoultNs law.
##$0 T(e 1apor ressure of Solutions Raoult2s +a,
(he vapor pressure of a solution is affected by the type of components present in it. 7n
an ideal solution of liquid-liquid solution$ the vapor pressure of the solution tends to obey
Raoults la!; the vapor pressure due to each component is proportional to the mole fraction of
that component in solution. (hat is$ for a solution consisting of liquids # and J$ the component
vapor pressures are
=# ? X#.=
o
#; =J ? XJ.=
o
J; =total ? =# E =J;
=# ? vapor pressure of liquid # in solution; X# ? mole fraction of # in solution$ and =
o
# ? vapor
pressure of pure solvent. =J ? vapor pressure of liquid J in solution; XJ ? mole fraction of J in
solution$ and =
o
J ? vapor pressure of pure solvent.
Solutions that obey Raoult"s la! are ideal solutions. )or example$ ben&ene and toluene form
ideal solutions. (he vapor pressure of each component and the total vapor pressure above the
solution can be calculated from the FaoultNs equations'
=b& ? Xb&.=
o
b&; =tol ? Xtol.=
o
tol;=total ? =b& E =tol
)or example$ in a ben&ene-toluene mixture where the mole fractions in the liquid are'
Xb& ? Xtol ? ..6..$ and the vapor pressure of pure ben&ene and toluene at 06
o
1 are :6./ torr
and 08.3 torr$ respectively$ the vapor pressures above the solution at this temperature will be'
=b& ? (..66. x :6./ torr) ? 3A.2 torr; =tol ? (..6.. x 08.3 torr) ? /3.0 torr;
=soln ? =b& E =tol ? (3A.2 E /3.0) torr ? 2/.8 torr.
6
(he vapor composition of this mixture at 06
o
1 is'
Gb& ? (=b&9=soln) ? (3A.292/.8) ? ..AA.; Gtol ? (=tol9=soln) ? (/3.092/.8) ? ..0-.;
4hen this vapor is condensed$ a liquid with the composition AA..> mole in ben&ene
and 0-..> mole in toluene is obtained. 7f this distillate is further distilled$ it will yield yet
another distillate with a composition that is richer in ben&ene (the more volatile of the two
components). 7f the process is repeated many times$ a pure ben&ene sample will be obtained
as the final distillate. (his is the principle involved in purification of liquid mixture by
fractional distillation.
ractical Uses
7deal liquid-liquid mixtures can be purified by fractional distillation$ which uses a tall
fractional distillation column. 7n fractional distillation the most volatile components are
obtained at the top of the column while the least volatile are collected as residues at the
bottom. 7t is the most important application in petroleum industries where components of
crude oils are separated into various petroleum products.
(he fractional distillation of an ideal mixture will yield pure components if the fractional
distillation column is tall enough to separate their vapor. )or a nonideal solution$ fractional
distillation subsequently leads to the formation of an azeotropic mixture$ which cannot be
further separated by distillation process because the composition of the vapor mixture is the
same as that of liquid mixture. )or example$ water-ethanol (1056,5) mixture forms an
a&eotrope mixture at the liquid composition of :6.2> in ethanol and 3.3> water$ by mass.
(his mixture has a constant boiling point of A8.0
o
1.
!xercise-3'
/. Jen&ene and toluene form an ideal solution at all proportion. (he vapor pressure of pure
ben&ene and pure toluene at 06
o
1 are :6./ and 08.3 mm5g$ respectively. 4hat is the
vapor pressure of a solution that contains 6... g ben&ene (mw A8.//) and 6... g
toluene (mw :0./-); 4hat is the composition of the vapor that is in equilibrium with the
above ben&ene-toluene solution at 06
o
1;
0. Styrene (1858) and ethylben&ene (185/.) form ideal mixture. 7f a mixture is composed of
-8> styrene and 20> ethylben&ene$ by mass$ at :.
o
1$ what is the composition of the
vapor in equilibrium with the liquid mixture. (he vapor pressure of styrene and
ethylben&ene at :.
o
1 are /-3 mm5g and /80 mm5g$ respectively.

COLLI(&TI"E PROPERTIES
Solutions containing nonvolatile solutes have physical properties significantly different
from the pure solvent. (he presence of nonvolatile solutes in solutions causes the following
physical changes to the solvent'
(he lowering of vapor pressure;
(he depression of free&ing point;
(he elevation of boiling point;
7
(he osmotic pressure exerted by the solution;

(hese are called the colli'ati!e properties of solutions$ which are properties that
depend only on the concentration of solute particles dissolved in the solution$ but not on the
type of solutes present. (he free&ing point depression ((f)$ the elevation of boiling point
((b)$ and the osmotic pressure of solution are the direct consequence of the lowering of vapor
pressure (=) of solvent by nonvolatile solutes.
# nonideal solution approaches ideal behavior under very dilute condition$ in which the
following simplified relationships can be used'
= ? =
o
- =$
= ? (/ Xs)=
o
? =
o
Xs=
o
= ? =
o
- = ? Xs=
o
(for non-electrolytes)
? iXs=
o
(for electrolytes)
= is called the lowering of solvent vapor pressure in solution$ and it is directly proportional to
the mole fraction of the dissolved solute. =
o
is the vapor pressure of pure solvent$ = is the
vapor pressure of solvent in solution$ Xs is the mole fraction of solute$ and i is vanMt 5off factor
for solutes that dissociate. i ? / for nonelectrolytes; for strong electrolytes in very dilute
solutions$ i is approximately equal to the total number of ions in a formula unit. )or example$ i
P 0 for very dilute +a1l solution.
T(e Freezin' oint 3epression and Ele!ation of 4oilin' oint
(he free#ing point depression$ (f$ is proportional to the molal concentration (m) of solution'
(f ? *fm (for non-electrolytes)
(f ? i*fm (for strong electrolytes)
(he elevation of boiling point$ (b$ for a dilute solution is proportional to the molal
concentration of the solution'
(b ? *bm$ (for non-electrolytes)
(b ? i*bm$ (for strong electrolytes)
*f and *b are called the free&ing point lowering constant and boiling point elevation constant$
respectively. 7n the above expressions$ solute concentrations are expressed in molal (m)$
which is mole of solute per kg of solvent.
*f and *b values of some solvents are given below'

Solvent ). =t$
o
1 *f$
o
19m J.=t$
o
1 *b$
o
19m

4ater . /.82 /.. ..60

Jen&ene 6.6 6./0 8../ 0.6
+itroben&ene 8./. 6.03
1arbon tetrachloride -0-.. -... A2.6 6..-
8
1hloroform -2-.6 3.A. 2/.0 -.2-
1arbon disulfide -///.6 -.8- 32.0 0.-3
1amphor /A:.8 -:.A 0.8.. 6.:6

!xercise-6
/. 1alculate the vapor pressure lowering$ =$ when /... m% of glycerol (1-58,-) is added to
6.... m% of water at 6..
o
1. #t this temperature$ the vapor pressure of pure water is
:0.6 torr and its density is ..:88 g9m%. (he density of glycerol is /.02 g9m%.
0. # radiator fluid mixture contains -... Bg of antifree&e ethylene glycol (1052,0) and 0.6.
Bg of water. 4hat is the boiling and free&ing points of the solution; ()or water$ $f ? /.82
o
19m; $b ? ..6/0
o
19m)
-. 4hat is the minimum concentration of ethylene glycol (1052,0) solution that will protect
the cooling system from free&ing at ...
o
1;
3. 4hen /.:0/ g of nicotine is completely dissolved in 38.:0 g of water$ the solution free&es
at -..36.
o
1. (a) 1alculate the molality of the solution. (b) 4hat is the molar mass of
nicotine; (c) 7f nicotine has the composition A3..> 1$ 8.A.> 5 and /A.- > +$ by mass$
determine its empirical and molecular formula.

5smotic ressure
7f a pure solvent and a solution containing a nonvolatile solute are separated by a semi
permeable membrane$ there will be a net movement of solvent molecules across the
membrane into the solution. (his spontaneous net flow of solvent molecules through a semi
permeable membrane from a pure solvent or a dilute solution into the more concentrated
solution is called osmosis. (he pressure that is needed to stop the net spontaneous flow of
solvent molecules across a semi-permeable membrane is called the osmotic pressure () of
the solution. )or a dilute solution$ osmotic pressure is given as$
? MF( ? (n9@)F($ (for non-electrolytes)$
? iMF( ? i(n9@)F( (for strong electrolytes)
(M is molar concentration of the solution)
7f a pressure greater than the osmotic pressure is applied to an aqueous solution$ water can
be forced out of the solution through the semi-permeable membrane. (his process is called
reverse osmosis$ which have been employed to obtain fresh water from seawater. 7t is a
process that requires energy.
!xercise-2'
/. 7f a solution contains /..6 g of sucrose (1/0500,//) per /... m%$ what is its osmotic
pressure at 06
o
1. 4hat concentration (in g9/... m% solution) of salt (+a1l) would
exhibit the same osmotic pressure. (#ssume +a1l dissociates completely.)
9
0. # 6... m% sample of an aqueous solution containing /..8 g of human serum albumin
(5S#) has an osmotic pressure of 6.86 mm5g at 0:8 *. 1alculate the molar mass of
5S#.

##$6 Colloids
%olloids are mixtures that is intermediate between a true solution and a heterogeneous
mixture. # colloidal mixture contains particles that are many times larger than the solvent
molecules$ but too small to be seen by an ordinary light microscope. 1olloidal particles are
usually dispersed in a homogeneous medium liBe water or air. (o differentiate a colloid from a
solution the terms dispersed substance and dispersing medium are used instead of solute and
solvent.
<any colloidal particles maybe composed of clusters of small particles that are held
together by intermolecular forces. Soaps and detergents are examples of colloidal particles
made up of clusters of small particles. 7n water$ soap and detergent molecules form clusters
called micelles$ which have inner hydrophobic regions. SmoBe is also clusters of small
particles.
Types of Colloids

1olloidal State of
particles <edium +ame !xample

"as %iquid )oam Suds on bear or soapy water$ whip cream$

shaving cream$ fire-fighting foam.
"as Solid )oam )oam rubber$ Styrofoam$ marshmallows$
sponge$ pumice.
%iquid "as #erosol )og$ clouds$ aerosol sprays.
%iquid %iquid !mulsion 5omogeni&ed milB$ mayonnaise
%iquid Solid !mulsion Jutter
Solid "as #erosol smoBe$ airborne particulates
Solid %iquid Sol 1ream$ milB of magnesia$ mud$ detergents$
many paints$ toothpaste$ Iell-,.
Solid Solid ruby glass

1olloids may also be classified as lyophobic (solvent hating)$ and lyophilic (solvent
loving). 7f the dispersion medium is water$ the colloids are referred to as hydrophobic or
hydrophilic. "elatin is an example of hydrophilic colloid.
1olloidal mixtures do not exhibit colligative properties because the concentration of the
dissolved particles are too low to exhibit any effect of the vapor pressure of the solvent.
5owever$ 1olloidal mixtures exhibit Tyndall effects$ the ability to scatter light so that the
beam going through the medium becomes visible.
10