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Solutions
Solutions are homogeneous mixtures of two or more
substances.
Dissolving medium is called the solvent.
Dissolved species are called the solute.
There are three states of matter (solid, liquid, and gas)
which when mixed two at a time gives nine different kinds of
mixtures.
Seven of the possibilities can be homogeneous.
Two of the possibilities must be heterogeneous.
Seven Homogeneous Possibilities
Solute Solvent Example
Solid Liquid salt water
Liquid Liquid mixed drinks
Gas Liquid carbonated
beverages
Liquid Solid dental amalgams
Solid Solid alloys
Gas Solid metal pipes
Gas Gas air
Solutions Page 77
Two Heterogeneous Possibilities
Solid Gas dust in air
Liquid Gas clouds, fog
Solutions Page 78
soluble in non - polar solvents. This is the first rule of
solubility "like dissolves like" e.g: benzene in CCI4
Solution Concentration:
Solutions Page 79
weight of solute
mass% x 100
total weight of solution
weight of solute
weight fraction
N.B total weight of solution
3) Molality
Molality is similar to but not the same as molarity. Molality,
m, is defined by,
Solutions Page 80
( )
N.B
Solutions Page 81
)
Solutions Page 82
b) Weight to volume expression:
1) Molarity (M):
• h d d solution.
•
• M = (W/M. wt) solute X (1000/V) solution
Solutions Page 83
b) If the density of the concentrated nitric acid
solution is 1.42 g/ml. What volume should be
used? M.wt. (HNO3) =63
Solution: a) 70 gm HNO3 l00 gm solution
W 1000 W 1000
M x 2 x
M.Wt 250 63 250
2 x 63 x 250
Mass of pure HNO3
1000
31.5 x 100
mass of HNO3 solution = 45.0 gm
70
b) ml cone. NHO3 = (45/1.42) = 31.7 ml cone. HNO3
Solutions Page 84
Solution:
W 1000 164.2 x 1000
M x 3.4
a) M.Wt solute Vml 60 x 800
b) d = 1.026g/ml V = 800 ml
W solution = V x d = 800 x 1.026 = 820.8 gm
W slvent = 820.8 - 164.2 = 656.6 gm
mass 1000 164.2 x 1000
m (Solute) x 4.17 m
M.Wt W(Solvent) 60 x 656.6
c) no. of acetic acid moles = 164.2 / 60 = 2.737 mole
no. of H2O moles = 656.6 / 18 = 36.44 mole
2.737
Mole fraction of acetic acid = 0.0699
2.737 36.44
36.44
Mole fraction of H2O = 0.9299
2.737 36.44
d) mole % acetic acid = 0.0699 x 100 = 6.99 %
mole % of H2O = 0.9299 x 100 = 92.99 %
164.2 x 100
e) percentage weight of acetic acid = 20 %
820.8
656.6 x 100
percentage weight of H2O= 80 %
820.8
Solutions Page 85
Try ?
1. Five grams of NaCl is dissolved in 25.0 g of H2O. What is
the mole fraction of NaCl in the solution? (Answer =0.0580)
2. What is the mole percent NaCl in the previous problem 1
(Answer = 5.80 mol %)
3. Ten grams of ascorbic acid (vitamin C), C6H8O6, is
dissolved in enough water to make 125 ml of solution.
What is the molarity of the ascorbic acid? (Answer = 5.80
mol %)
4. What is the molality of NaCl in the solution in the previous
problem 1? (Answer = 3.42 m)
5. What is the mass percent of NaCl in the solution in the
previous problem 1? (Answer = 16.7 %)
• Principles of Solubility
Solutions Page 86
3. The temperature.
4. The pressure (for gases).
1. Solute-Solvent Interactions:
Solutions Page 87
bonds in both pure liquids are re-established in the
mixture. However, not all alcohols are miscible with
water. Why? The number of carbon atoms in a chain
affects solubility. The greater the number of carbons in
the chain, the more the molecule behaves like a
hydrocarbon. Thus, the more C atoms in the alcohol,
the lower its solubility in water. Increasing the number
of –OH groups within a molecule increases its
solubility in water. The greater the number of –OH
groups along the chain, the more solute-water H-
bonding is possible.
4. Generalization: “Like dissolves like”. Substances
with similar intermolecular attractive forces tend to be
soluble in one another. The more polar bonds in the
molecule, the better it dissolves in a polar solvent. The
less polar the molecule the less likely it is to dissolve in
a polar solvent and the more likely it is to dissolve in a
nonpolar solvent..
Solutions Page 88
than dissolving. The mole fraction of pentane, C5H12 in a
saturated water solution is only 0.00003. Few organic
compounds that dissolve readily in water, most contain - OH
groups. Three familiar examples are methyl alcohol, ethyl
alcohol, and ethylene glycol, all of which are soluble in water in
all proportions.
H H H H H
H C OH H C C OH H C C H
H H H OH OH
Solutions Page 89
Since solubility is an equilibrium concentration, we can apply Le
Chateher"s principle in order to find out what happens when the
temperature of a saturated solution is changed. It is important to
know whether the dissolving process is
exothermic
Solute + solvent → +h or
endothermic
Solute + +h →
The heat of solution is defined as H for the dissolving process,
and so is equal to H solution - (H solute + H solvent). Therefore, for the
exothermic case, ΔH solution is negative, and for the endothermic,
positive.
Consider now a saturated aqueous solution of potassium iodide
with excess KI(s) present. For KI, ΔH solution = 21 kJ mol -1, so we
know that KI dissolves in water with the absorption of heat and
can write the saturation equilibrium equation as
21 kJ + KI(s) K+ + I-
Solutions Page 90
added heat (and some of the excess solid KI) and (2)
increasing the concentration of K+ and I- ions in solution.
After equilibrium has been reestablished at a higher
temperature, the concentration of dissolved KI has become
higher, that is, the solubility of KI increases with increasing
temperature.
If we raise the
temperature of a
saturated solution of
LiI, the equilibrium
shifts to the left (1)
using up some of the
added heat (and I-
and Li+ ions in
solution) and , (2)
forming more solid Lil.
Solutions Page 91
(We observe the precipitation of some Lil out of solution.)
Solutions Page 92
chlorine) is less soluble at the boiling point and is removed from
the water.
Cg - solubility of gas
Cg kPg
Solutions Page 93
Pg - the partial pressure of the gas
k-H ’ w
Solutions Page 94
PO2 = P total - PH2O = 101-3 = 98 kPa
a) Ideal Solution:-
e.g: (n - heptane / n - hexane)
(chlorobenzene / brombenzene)
Solutions Page 95
1) The force of attraction between all molecules are
identical i.e. the attraction force is not affected by
addition of other components A - A = B-B = A - B.
2) No heat is evolved or absorbed during mixing i.e. ∆H
soln. = Zero
3) The volume of solution is the sum of volumes of the
two liquids.
4) The solution obeys RaouLt's law.
At constant
temperature the
partial vapor
pressure of liquid
component in
ideal solution is
proportional to the
mole fraction of
this constituent in
Figure (1): Vapor pressure of ideal
solution (Figure 1).
solutions
Solutions Page 96
At constant T
Solutions Page 97
Or
Pt = ( - ) (5)
N.B Composition of solution % XA and % XB.
% A= XA x 100 % B = XB x 100
Solution:
The total number of moles is 8.0. therefore
X heptane = 3.0/8.0 = 0.375
X octane = 5.0/8.0 = 0.625
Total = X heptane . Po heptane + X octane. Po octane
= 0.375 x 0.12 +0.625 x 0.04
= 0.045 atm + 0.026 atm.
= 0.071 atm.
Solutions Page 98
Example 4.7 : Assuming ideality, calculate the vapor
pressure of 1.0 m solution of a non - volatile, on
dissociating solute in water at 50°C. The vapor
pressure of water 50°C is 0.122 atm.
Solutions Page 99
pressure of pure acetone and pure CHCI3 at 35°C
are 345 and 293 torr, respectively.
Solution:
W 5.81
n acetone = 0.1 mole
M.Wt 58.1
11.9
n CHCl3= 0.1 mole
119
XCHCl3 = 0.5
• h h w h h
ideal.
• h b d 6 h h d
= 319 this is a negative deviation from Roault's law.
Psolvent X solventPsolvent
0
X solute 1 - X solvent
Psolvent X solute Psolvent
0
Examples 4.9
The vapor pressure of water is 17.5 torr at 20°C. Imagine
holding the temperature constant while adding glucose,
C6H12O6, to the water so that the resulting solution has XH2O
= 0.80 and XGlu = 0.20.
Try ?
1. Glycerin, C3H8O3, is a nonvolatile nonelectrolyte with a
density of 1.26 g/mL at 25°C. Calculate the vapor
pressure at 25°C of a solution made by adding 50.0
mL of glycerin to 500.0 mL of water. The vapor
pressure of pure water at 25°C is 23.8 torr
2. The vapor pressure of pure water at 110°C is 1070
torr. A solution of ethylene glycol and water has a
vapor pressure of 1.00 atm at 110°C. Assuming that
Tb K b m
where : Tb boiling point elevation
m molal concentrat ion of solution
K b molal boiling point elevation constant
for the solvent
Example 4.9
Example 4.10
Automotive antifreeze consists of ethylene glycol, C2H6O2,
a nonvolatile nonelectrolyte. Calculate the boiling point of a
25.0 mass percent solution of ethylene glycol in water.
Solution:
Boiling point = (normal b.p of solvent + ∆ T
Tf K f m
where : Tf freezing point depression of solvent
m molal concentrat ion of soltuion
K f freezing point depression constant for solvent
Tf K f m
Tf (1.86 0 C/ m )(2.50m )
Tf 4.65 0 C
Freezing Point of solution = 0.00 0 C - 4.65 0 C = - 4.65 0 C
MRT
where : = osmotic pressure in atm
n
M = molar concentrat ion of solution
V
L atm
R = 0.0821
mol K
T = absolute temperatur e
For very dilute aqueous solutions, molarity and
molality are nearly equal. mRT
Mm for dilute aqueous s olutions o nly
Osmotic pressures can be very large.
For example, a 1 M sugar solution has an
osmotic pressure of 22.4 atm or 330 p.s.i.
Since this is a large effect, the osmotic pressure
measurements can be used to determine the
molar masses of very large molecules such as:
Polymers
Biomolecules like
proteins
Ribonucleotides
Application of osmosis
1) Revesse osmosis: When an external pressure is
applied over the solution, the solvent is forced in a
direction contrary to that normally observed. This
process called reverse osmosis is used to secure pure
water from salt water. This is used in desalination of
seawater to be suitable for drinking.
?g 1.00 g 1L
4
6.67 10 4 g mol
mol 0.100 L 1.50 10 M
typical of small proteins
Try ?