CHEMY 101

CHAPTER 12
Physical Properties of Solutions
CHCHAPTER OUTLINE

12.1 Types of Solutions

12.3 Concentration Units

12.4 The Effect of Temperature on Solubility

12.5 The Effect of Pressure on the Solubility of Gases

12.6 Colligative Properties of Nonelectrolyte Solutions

12.7 Colligative Properties of Electrolyte Solutions

12.8 Colloids
12.1:Type of Solutions

Solution is a homogeneous mixture of two or more substances.

2
A saturated solution contains the maximum amount of a solute
that will dissolve in a given solvent at a specific temperature.

An unsaturated solution contains less solute than the solvent

has the capacity to dissolve at a specific temperature.

A supersaturated solution contains more solute than is present

in a saturated solution at a specific temperature.

Crystallization is the process in which dissolved solute comes

out of solution and forms crystals.
 A SUPERSATURATED SOLUTION

Solute immediately … until all of the

begins to crystallize … excess solute has
A single “seed precipitated.
crystal” of
solute is added.

• Supersaturated
➢ Solvent holds more solute than is normally possible at that
temperature.
 12.3: CONCENTRATION UNITS
➢ The concentration of a solution is the amount of solute
present in a given quantity of solvent or solution.
❑The concentration of a solution is expressed as:
➢Molarity (M)
➢Molality (m)
➢% mass or (m/m) %
➢Part per million (ppm)
➢Part per billion (ppb)
➢Mole fraction (x)
Molarity (M)
The number of moles of solute per liter of
solution (mole/L)

moles of solute
M =
volume of solution (L)

mass of solute (g)

M =
MM X Volume of solution(L)
Example:
A stock solution of CuSO4 is prepare by adding 40 g of
CuSO4 to enough water to make 500 mL of solution
a) Find the molarity of the CuSO4 stock solution
b) How would you prepare 1.5 L of 0.1 M solution from the
stock solution. [MM = 159.6]
Mass (g) 40 x 1000 = 0.5 M
a) M= =
159.6 x 500
MM X V(L)

b) Mi = 0.5 Mf = 0.1 Vf = 1.5 L Vi = ? L

MiVi = MfVf MfVf 0.200 x 0.06

Vi = = = 0.3 L = 300 mL
Mi 4.00
300 mL of stok + 1200 mL of water = 1500 mL of solution
(1.5 L)
Molality (m)
The number of moles of solute per kilogram of
solvent. Its unit is mole/Kg

moles of solute
m =
mass of solvent (kg)

mass of solution = mass of solvent + mass of solute

mass of solution (g)

Solution density (d) d =
volume of solution (mL)
Example:
What is the molality of a solution prepared by adding 6 g
of glucose to 112 g of water? [MM (glucose) = 180.16
g/mol]
Mass (g) 6
n (glucose) = = = 0.0333 moles
MM 180.16

mass of solvent (water) in kg = 112 g/1000 = 0.112 kg

moles of solute 0.0333 moles

m = = = 0.297 m
mass of solvent (kg) 0.112 kg
 Mass Percent
mass of solute x 100%
mass % =
mass of solution
mass of solute
= x 100%
mass of solute + mass of solvent

➢ 37 mass % HCl means 37 g of HCl is present in 100 g of the

solution.
➢ It is prepared by dissolving 37 g of HCl + 63 g of water.
Example:
What is the mass% of NaCl in the solution prepared by
dissolving 24 g of NaCl in 152 g of water?

mass of solute
mass % = x 100%
mass of solute + mass of solvent
24 g
mass % (NaCl) = x 100% = 14 %
24 g + 152 g
Parts per million (ppm)
The number of particles of solute per one million particles
of solution.
ppm = mass of solute x 106
mass of solution
➢Very low solute concentrations are expressed as ppm

For any solution 1 ppm = mg/kg = µg/g

❖ As the density of water is 1
For aqueous solution (water)
1 ppm = mg/L = µg/mL
Example:
What is the ppm of Na + ions contained in a solution
prepared by dissolving 2 mg Na + ions and 6 g of glucose in
112 g of water?

mass of solution = mass water + mass glucose + mass Na+

mass of solution = 112 g + 6 g + (2 X 10-3) g = 118 g

2 X 10 -3
ppm = mass of solute x 106 = x 106 = 17 ppm
mass of solution 118
Parts per billion (ppb)
The number of particles of solute per one billion particles of
solution.
ppb = mass of solute x 109
mass of solution
For aqueous solution (water), 1 ppb = µg/L

Example:
Find the concentration in ppb of a solution in which
9.6 x 10-6 g of NaCl has been dissolved making a
solution with a volume of 2.0 L.

9.6 X 10 -6
ppb = mass of solute 9
x 10 = x 10 9
mass of solution 2000
= 4.8 ppb
Mole Fraction (X)

moles of component A per moles of all components.

moles of A (nA)
XA =
sum of moles of all components (nA+ nB + nC +….)

❖ The sum of mole fractions of all components is one

XA + XB + XC + …….. = 1

Mole % of A = XA . 100%
 Example:
What is the mole fraction and mole % of hydrogen
peroxide (H2O2) in a 30 % by mass aqueous solution?
[MM (H2O) = 18 g/mol, MM (H2O2) = 34 g/mol]

30 mass % H2O2 means Mass H2O2= 30 g Mass H2O = 70 g

70 g 30 g
n (H2O) = = 3.88 mol n (H2O2)= = 0.882 mol
18 34
ntot = nH 2O 2 + nH 2O
= 0.882 mol + 3.88 mol = 4.76 mol
nH 2O 2 0.882 mol
XH 2O 2 = =
ntot 4.76 mol
= 0.185
 Conversions Between Concentration Units

• Conversions are straightforward when the exact amount of

solution is decided
– Depend on the unit of concentration initially used
 Convert Molarity (M) to Molality (m)
Example:
What is the molality of a 5.86 M ethanol (C2H5OH) in
1 L solution whose density is 0.927 g/mL? [MM
(C2H5OH) = 46.07 g/mol]
moles of solute Mass (g) mass
M = = 5.86 =
liters of solution MM X V (L) 46.07 X 1
Mass = 270 g ethanol
Mass (g) mass
d = 0.927 = Mass = 927 g solution
V (mL) 1000 mL
mass of solvent = mass of solution – mass of solute
= 927 g – 270 g = 657 g = 0.657 kg
moles of solute 5.86 moles C2H5OH
m = = = 8.92 m
mass of solvent (kg) 0.657 kg solvent
CONVERT % MASS TO MOLARITY (M)

Use this relation

d X 1000 % mass
M= X
MM 100
Example:
What is the Molarity of a 95% acetic acid solution?
(density = 1.049 g/mL, MM = 60.05 g/mol)

1.049 X 1000 95
M = X
60.05 100
M = 16.6 mole/L
 CONVERT % MASS TO MOLALITY (M)

Use this relation

% mass 1000
m = X
MM (100 ‒ %)

Example:
What is the Molality of a 37.7% HClsolution? (MM = 36.46
g/mol)
37.7 1000
m = X
36.47 (100 ‒ 37.7)
m = 16.6 mole/kg
 CONVERT PPM TO MOLARITY (M)

Use this relation

ppm
M= X 10‒3
MM

Example:
What is the Molarity of 40 ppm NaOH solution? (MM = 40
g/mol)

40
M = X 10-3
40
M = 0.001 mole/L
CONVERT MOLE FRACTION (X A ) TO MOLALITY (M)

XA . 103
Use this relation m =
(1 – XA) . MMsolvent

A = component in solution (solute)

Solvent = Water , MMsolvent = 18

Example: The mole fraction of an aqueous solution of glucose

(C6H1206) is 0.15. What is the molality of glucose in the

solution? (MM = 40 g/mol)

0.15 x 103
m = m = 9.8 mole/Kg
(1 – 0.15) x 18
 CONVERT MOLE FRACTION (X A ) TO MOLARITY (M)

XA . d . 103
Use this relation M=
XA. MMA+ (1 – XA) . MMsolvent

A = component in solution (solute)

MMA = molar mass of solute A
Solvent = Water , MMsolvent = 18
Example:
The mole fraction of an aqueous solution of Na2S04 is 0.14. What
is the molarity of Na2S04 in the solution?
[d = 2.66 g/mL, MM(Na2S04) = 142.04 g/mol]

M = 0.14 x 2.66 x 103 = 13.5 mole/L

(0.14 x 142.04) + (1 – 0.14) x 18
Principles of Solubility

➢ The interaction between solute and solvent molecules is

known as Solvation or Dissolution or solubility.
➢ When water is the solvent, it is also known as Hydration
and the resulting solution is called aqueous solution.

In most solids, solubility increases with an

increase in temperature
 SOLUBILITY OF COMPOUNDS
➢The general rule is “Like dissolves Like”.
➢Ionic and polar solutes are soluble in polar solvents
➢Non-polar solutes are soluble in non-polar solvents
➢Examples:

1. Water (polar) and methanol (polar) are soluble or

miscible.
2. Oil (non-polar) and benzene (non-polar) are soluble or
miscible.
3. Water (polar) and oil or petroleum or hydrocarbons (non-
polar) are not soluble or immiscible.
12.4 THE EFFECT OF TEMPERATURE ON SOLUBILITY

Solubility is the maximum amount of a solute that will

dissolve in a given quantity of solvent at a specific
temperature. Temperature affects the solubility of most
substances.
 12.4 TEMPERATURE AND SOLUBILITY OF GASES

❑ Solubility of gases decreases as the

temperature increases.

➢ So, many fish can survive in cold water.

Dissolved oxygen is
➢ There is not enough dissolved oxygen in released as water is
warm water to sustain them. heated.
12.5 PRESSURE AND SOLUBILITY OF GASES

An increase in pressure at a set temperature results

in the increased solubility of a gas.
 PRESSURE AND SOLUBILITY OF GASES

Henry’s Law

❖At a constant temperature, the solubility (S) or concentration (C)

of a gas dissolved in a liquid is directly proportional to the
pressure of the gas (Pgas) in equilibrium with the solution.

Sgas or Cgas = k Pgas Pgas = xgas·Ptotal

➢ Pgas is the partial pressure of the gas over the solution

➢ Cgas is the concentration of the gas in solution
➢ k is a constant of the gas liquid system
Example:
The solubility of pure nitrogen in blood at body
temperature, 37°C, and one atmosphere is 6.2 × 10-4 M. If
a diver breathes air ( XN2 = 0.78 ) at a depth where the total
pressure is 2.5 atm, calculate the concentration of
nitrogen in his blood.

Answer

1. K can be found using Henry’s law and the solubility for pure N2
at 1.00 atm
CN 2 = kPN 2
CN 2 6.2  10 M –4
k= =
PN 2 1.00 atm
= 6.2  10 M/atm
–4
2. The value of PN2 can be found when Ptot is 2.5 atm using the
relationship between mol fraction and partial pressure

PN 2 = XN2 Ptot
PN 2 = XN 2 Ptot = (0.78)(2.5 atm)
= 2.0 atm
3. Substitution in Henry’s law to find new CN 2 at the higher
pressure
CN 2 = kPN 2
M
–4
CN2 = 6.2× 10 × 2.0 atm
atm
= 1.2×10 –3 M
12.6 COLLIGATIVE PROPERTIES OF NONELECTROLYTES

❑Colligative properties of a solution depend only on the

number of solute particles in solution, and not on the
nature of the solute particles.

❑Will examine four colligative properties of solutions:

1. Vapor pressure lowering

2. Freezing point depression
3. Boiling point elevation
4. Osmotic pressure
1- Vapor Pressure Lowering
➢The vapor pressure of solvent above a solution is
lowered as compared to the pure solvent state.
➢In other words, the vapor pressure of a solution is less than
that of the pure solvent.

Raoult’s Law Psolution = Xsolvent · P°solvent

P(solution) = vapor pressure of solution
P°(solvent) = vapor pressure of pure solvent
X(solvent) = mole fraction of pure solvent
❖ If the solution contains only one solute
X1 = 1 – X2 P 0 - P1 = DP = X2 P 0
X2 = mole fraction of the solute
Pressure unit 1 atm = 760 mm Hg (torr)
Example
An aqueous solution contains 0.42 mole fraction of ,
Sugar,. Calculate the vapor pressure of the solution
at 25°C. The vapor pressure of pure water at 25°C 5
23.76 mm Hg).

❖Mole fraction of solvent (water)

X (sugar) +X (H2O) =1
X (H2O) =1–X (sugar) = 1 – 0.42 = 0.58

❖Pressure of solution

Psolution = xsolv · P°solv

= 0.58 x 23.76 = 18.8 mmHg
Example
A solution contains 82 g of glucose, C6H12O6, in 322 g
of water. Calculate the vapor pressure of the solution
at 25°C. Vapor pressure of pure water at 25°C 5 23.76
mm Hg).
❖Moles solute ngloucose = 82/180 = 0.455 mol
❖Moles solvent nH2O = 322/18 = 17.9 mol
❖Mole fraction of solvent
nH 2 O 17.9 mol
X H2O = = = 0.975
nH 2 O + n glucose (17.9 + 0.455) mol
❖Pressure of solution
Psolution = xsolv · P°solv
= 0.975 x 23.76 = 23.17 mmHg
2- FREEZING POINT DEPRESSION

❖ The freezing point of the solvent in solution is depressed as compared to

the pure solvent state.
❖ In other words, the freezing point of a solution is lower than that of the pure
solvent.

DTf = T°f(solvent) – Tf(solution)

= Kf × m
ΔTf = freezing point depression
T°f(solvent) = freezing point of pure solvent
Tf(solution) = freezing point of solution
Kf = constant
m = molality of the solution
 3-BOILING POINT ELEVATION

❖ The boiling point of the solvent in solution is elevated as compared to the

pure solvent state.
❖ In other words, the boiling point of a solution is higher than that of the pure
solvent.

DTb = Tb(solution) – T°b(solvent)

= Kb × m
ΔTb = boiling point elevation
T°b(solvent) = boiling point of pure solvent
Tb(solution) = boiling point of solution
Kb = constant
m = molality of the solution
FREEZING POINT DEPRESSION AND BOILING POINT
ELEVATION

DTf = Kf × m DTb = Kb × m
Example
What are the boiling point and freezing point of a solution
prepared by dissolving 2.4 g of biphenyl (MM = 154) in 75 g
of benzene? (T°b = 80.1 °C, T°f = 5.5 °C , Kb = 2.53 °C/m , Kf =
5.12 °C/m).
Solvent = benzene; Solute = biphenyl n = 2.4/154 = 0.016

moles of solute 0.016

m = = = 0.208
mass of solvent (kg) 75 x 10-3

ΔTb = m kb = 0.208 x 2.53 = 0.526 °C

ΔTb = Tb – T°b Tb = ΔTb + T°b
Tb = 80.1 + 0.526 = 80.6 °C
ΔTf = m kf = 0.208 x 5.12 = 1.06 °C
ΔTf = T°f – Tf Tf = T°f – ΔTf
Tf = 5.5 – 1.06 = 4.4 °C
Example
A solution prepared by dissolving ethylene glycol
HO(CH2)2OH in water. The boiling point of this solution is 103
°C .What is the freezing point of the solution.
[T°f = 0 °C, Kf = 1.86 °C/m, T°b= 100 °C, Kb= 0.52 °C/m].

ΔTb = Tb – T°b = 103 – 100 = 3

ΔTb = m kb m = ΔTb / kb = 3/0.52 = 5.7

ΔTf = m kf = 5.7 x 1.86 = 10.6 °C

ΔTf = T°f – Tf
Tf = T°f – ΔTf
Tf = 0 – 10.6 = – 10.6 °C
Example
What is the freezing point of a solution containing 50 mL of
ethylene glycol (d = 1.12 g/mL) in 50 g of water? The molar
mass of ethylene glycol is 62.01 g and the density of solution
is 1.12 g/mL) . [T°f = 0 °C, Kf = 1.86 °C/m].

d = mass/V(mL) mass = d x V = 1.12 x 50 = 56 g

n = 56/62.01 = 0.9

moles of solute 0.9

m = = = 18 m
mass of solvent (kg) 50 x 10-3

ΔTf = m kf = 18 x 1.86 = 33.7 °C

ΔTf = T°f – Tf Tf = T°f – ΔTf
Tf = 0 – 33.7 = – 33.7 °C
 4- OSMOTIC PRESSURE
❖Osmosis is the flow of solvent molecules through a porous
membrane from a dilute solution to a more concentrated one.
❖A semipermeable membrane allows the flow of solvent
molecules but blocks the passage of solute molecules.
❖Osmotic pressure (p) is the pressure required to stop osmosis.
Van’t Hoff Equation

p = (n/V)RT = M RT

p = osmotic pressure
V= volume of solution in liter
n= number of moles
R = gas constant (0.0821 L.atm/mol.K)
M= molarity of the solution
T = temperature (K)
Example
Calculate the osmotic pressure at 15 °C of a solution
prepared by dissolving 50 g of sugar (MM = 342.3 g/mol), in
enough water to form one liter of solution.
(R = 0.0821 L · atm/mol · K)
Answer
n = 50/342.3 = 0.146 mol

M = n/V(L) = 0.416/1 = 0.416 M

p = MRT = 0.416 x 0.0821 x (273 + 15) = 3.45 atm

Example: A solution made up of 1 g of an unknown solute and 275
mL of water has an osmotic pressure of 662.72 mmHg at 25 °C.
What is the molar mass of the unknown solute?
(R = 0.0821 L.atm/mol.K, 1 atm = 760 mm Hg)

p = 666.72/760 = 0.872 atm, T (K) = (273 + 7) = 300 K

0.872
M= p / RT = = 0.04 mol/L
0.0821 x 300

M = n / V(L) V = 275 mL = 0.275 L

n = M x V(L) = 0.04 x 0.275 = 0.011 mol
n = mass (solute) / molar mass (MM)
MM = mass / n = 1 / 0.011 = 91 g/mol
 12.7 COLLIGATIVE PROPERTIES OF
ELECTROLYTES

❑ Electrolytes differ from nonelectrolytes in dissociation

in process.
➢ Dissolving one mole of glucose (nonelectrolyte) in water
results in one mole of solute molecules

1 mol sugar solution 1 mol sugar molecules

➢ On the other hand, dissolving one mole of NaCl (electrolyte)

in water results in 2 mole of ions
1 mol NaCl solution 1 mol Na+ ions + 1 mol Cl- ions
1mol NaCl solution 2 mol ions in solution
❖ Van’t Hoff factor (i):
Is the number of moles of ions in solution per mole of solute .

➢ For sugar and other nonelectrolyte i = 1

➢ For electrolyte i should be
NaCl 2
MgSO4 2
CaCl2 3
Cr(NO3 )3 4
FeCl3 4
Fe2(SO4)3 5
❖ For electrolytes, we calculate DTb, DTf and p
by multiplying i in the rules

0
Vapor-pressure Lowering DP = i X2 P

Boiling-Point Elevation DTb = i Kb m

Freezing-Point Depression DTf = i Kf m

Osmotic Pressure (p) p = i MRT

Example
calculate the freezing points of 0.2 m aqueous solutions of
KNO3 and Cr(NO3)3

KNO3 (s) → K + (aq) + NO3 – (aq)

• KNO3
2 ions: 1K + and NO3 – ; i = 2
ΔT = ik f m = 2(1.86°C/m)(0.20 m) = 0.74°C
Tf = Tf ° – ΔT = 0°C –0.74°C= – 0.74°C
Cr(NO3 )3 (s) → Cr3 +(aq)+ 3NO3 – (aq)
• Cr(NO3)3
4 ions: 1 Cr 3+ and 3 NO3 – ; i = 4
ΔT= ik f m = 4(1.86°C/m)(0.20 m) = 1.5°C
Tf = Tf °– ΔT = 0°C –1.5°C = –1.5°C
Example
Calculate the osmotic pressure at 20 °C of a solution prepared
by dissolving 65 g of Na2SO4(MM = 142.04 g/mol), in enough
water to form 500 mL of solution.
(R = 0.0821 L · atm/mol · K)

n = 65/142.04 = 0.46 mol

M = n / V(L) = 0.46 / 0.5 = 0.9

For Na2SO4 → 2 Na + and 1 SO 2-

4 i=3

Π = iMRT = 3 x 0.9 x 0.0821 x 293 = 65 atm

Example 12.12
The osmotic pressure of a 0.010 M potassium iodide (KI)
solution at 25°C is 0.465 atm. Calculate the van’t Hoff
factor for KI at this concentration.

Answer

𝝅 = 𝒊 𝑴𝑹𝑻

i = 𝝅 / MRT
0.465 atm
i=
(0.010M) (0.0821atm/K. mol) (298K)

i = 1.90
12.8 COLLOIDS

The solutions discussed so far are true homogeneous mixtures.

Now consider what happens if we add fine sand to a beaker of
water and stir.

The sand particles are suspended at first but then gradually settle
to the bottom. This is an example of a heterogeneous mixture.
Between these two extremes is an intermediate state called a
colloidal suspension, or simply, a colloid.
12.8 COLLOIDS
A colloid is a dispersion of particles of one substance
(the dispersed phase) throughout a dispersing medium made
of another substance
Colloidal particles are much larger than the normal solute
molecules; they range from 1 × 103 pm to 1 × 106 pm.
Also, a colloidal suspension lacks the homogeneity of an
ordinary solution.
Hydrophilic and Hydrophobic Colloids
Hydrophilic (water-loving)
Hydrophilic colloids are usually solutions containing extremely
large molecules such as proteins. In the aqueous phase, a protein
like hemoglobin folds in such a way that the hydrophilic parts of
the molecule, the parts that can interact favorably with water
molecules by ion-dipole forces or hydrogen-bond formation, are
on the outside surface

Hydrophilic groups on the surface of a large

molecule such as protein stabilizes the molecule in water.
 hydrophobic (water-fearing)

A hydrophobic colloid normally would not be stable in water,

and the particles would clump together, like droplets of oil in
water merging to form a film of oil at water’s surface.

hydrophobic colloids can be

stabilized is by the presence of
other hydrophilic groups on their
surfaces.
Consider sodium stearate, a soap
molecule that has a polar head
and a long hydrocarbon tail that
is nonpolar
End of Chapter 12