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DH19TP_GROUP 1
Nguyen Thi Ngoc Han 19125513
Nguyen Thi Hoang Luong 19125517
Tran Thu Thao 19125530
Tran Thi Hai Yen 19125539
Module 2:
Solution and their physical
properties
Presentation Outline
1 Describe the solution.
5 Describe how temperature and
pressure affect solubility.
2 6
Express concentrations of Describe the four colligative
solutions in terms of molality and properties of solutions and some of
mole fraction. their applications.
7
Carry out calculations involving the four
3
Describe the factors that favor the colligative properties of solutions: lowering
dissolution process. of vapor pressure , boiling point elevation,
freezing point depression and osmotic
pressure.
4
Describe the dissolution of solids in
8
Use colligative properties to
liquids, liquids in liquids, and gases in determine molecular weights of
liquids. compound.
What is solution?
Definition of solution
• A solution is defined as a
homogeneous mixture of
substances in which no settling
occurs.
• A solution consists of a solvent and
one or more solutes,
whose proportions vary from one
solution to another.
• The solvent is the medium in
which the solutes are
dissolved. The fundamental units of
solutes are usually ions
or molecules.
Solubility
• Solubility of a substance is defined as the amount of the substance that will dissolve in
a particular solvent.
• Solubilities vary tremendously.
• At one extreme, some substances form solutions in all proportions and are said to be
miscible. For example, acetone and water can be mixed in any proportion, from pure
water to pure acetone.
• At the other extreme, a substance may be insoluble in another. One example is
common salt, NaCl, whose solubility in gasoline is virtually zero.
Solubility is based on:
Pressure applied Temperature of Nature of the solvent
to the system the solution and solute interaction.
Determinants of solubility
• Many combinations display solubility that is between the two extremes of miscible and
insoluble. In other words, the substance dissolves, but there is a limit to the amount of
solute that will dissolve in a given amount of solvent.
x 100
For example, a solution that is 10% calcium gluconate Ca(C6H11O7)2 ,by mass contains 10
grams of Ca(C6H11O7)2 in 100 grams of solution. This could be described as 10 grams of
calcium gluconate in 90 grams of water.
Percent by volume
x 100
Parts per Million, Parts per Billion, and Parts per Trillion
In solutions where the mass or volume percent of a component is very low, we
often switch to other units to describe solution concentration.
Note:
1 ppm = 1 mg/L,
1 ppb = 1 mg/L,
1 ppt = 1 ng/L.
1.0 L x 1.0 g/mL = 1000 g
ppm, ppb, and ppt are properly m/m or v/v.
Molarity vs Molality
The Molarity, M, of a solution is defined as the number of moles of the solute per liter of
solution.
Molarity =
The molality, m, of a solution is defined as the number of moles of the solute per
kilogram of solvent.
Molality =
Mole Fraction and Mole Percent
x=
The sum of the mole fractions of all the solution components is 1.
x1 + x2 + x3+ ... + xn = 1
The mole percent of a solution component can be calculated as:
Mole % i = xi x100%
Normality
– For acid-base reactions, an equivalent is the amount of substance that will react or form
1 mole of hydrogen
(H+) or hydroxide (OH-) ions.
– For redox (oxidation-reduction) reactions, an equivalent is the amount of substance that
will react or form 1 mole of electrons.
Normality =
N= nM
Percent by volume
An ethanol-water solution is prepared by
dissolving 10.00 mL of ethanol,
CH3CH2OH (d = 0.789 g/mL), in a
sufficient volume of water to produce
100.0 mL of a solution with a density of
0.982 g/mL. What is the concentration of
ethanol in this solution expressed as a)
volume percent; b) mass percent; c)
mole fraction; d) mole percent; e)
molarity; f) molality?
Answer
a)Volume percent ethanol
Volume percent ethanol
Ans.
Spontaneity of the dissolution process
- The energy change that accompanies a dissolution process is called the heat of
solution, ∆Hsolution. It depends mainly on how strongly solute and solvent particles
interact.
- The main interactions that affect the dissolution of a solute in a solvent follow:
+ Weak solute–solute attractions favor solubility.
+ Weak solvent–solvent attractions favor solubility.
+ Strong solvent–solute attractions favor solubility.
This schematic representation
of dissolution shows a
stepwise process involving the
endothermic separation of
solute and solvent species
(Steps 1 and 2) and
exothermic solvation (Step 3).
Intermolecular forces in mixtures
∆Hsolution = 0
-Ideal solution
Forces are similar between all
combinations of components.
Ideal solution
Benzene Toluene
Non-ideal solution
∆Hsolution < 0
Non-ideal Solution
- The general features of solubility are summarized by the expression: like dissolves like.
- Substances that dissolves in each other usually have similar types of intermolecular
interactions.
- One substance dissolves in another if the forces of attraction between the solute and the
solvent are similar to the solvent-solvent and solute-solute interactions.
Dissolution of liquids in liquids
Water and methanol are alike in that both substances contain O-H groups that form
hydrogen bonds readily. When these liquids are mixed, H2O... H2O hydrogen bonds and
CH3OH... CH3OH hydrogen bonds break, but H2O...CH3OH hydrogen bonds form.
The net result is that the degree of hydrogen bonding in the solution is about the same as
in either of the pure liquids, making these two liquids miscible.
Octane
Dissolution of liquids C8H18
Vitamin D
Solubility of solids: ionic solids
• The ability of an ionic solid to go into solution depends most strongly on its crystal
lattice energy, or the strength of attractions among the particles making up the solid.
• Crystal lattice energies are always negative
M(g) + X(g)→ MX(s) + energy
• If the solvent is water, the energy that must be supplied to expand the solvent includes
that required to break up some of the hydrogen bonding between water molecules.
• The third major factor contributing to the heat of solution is the extent to which solvent
molecules interact with particles of the solid.
• The process in which solvent molecules surround and interact with solute ions or
molecules is called solvation. When the solvent is water, the more specific term is
hydration.
Solubility of solids : ionic solids
A cluster of water molecules surrounds each ion in solution. Notice how the water
molecules are oriented so that their dipole moments align with charges of the ions. The
partially negative oxygen atoms of water molecules point toward cations, whereas the
partially positive hydrogen atoms of water molecules point toward anions.
Solubility of solids: ionic solids
• Hydration energy is defined as the energy change involved in the (exothermic)
hydration of one mole of gaseous ions.
Mn+(g) + xH2O → M (H2O)xn+ + energy (for cation)
Xy-(g) + rH2O → X (H2O)ry- + energy (for cation)
• Hydration is usually highly exothermic for ionic or polar covalent compounds, because
the polar water molecules interact very strongly with ions and polar molecules.
• The overall heat of solution for a solid dissolving in a liquid is equal to the heat of
solvation minus the crystal lattice energy.
∆Hsolution = (heat of solvation) - (crystal lattice energy)
Solubility of solids: ionic solids
• Magnitudes of crystal lattice and hydration energies generally increase with increasing
charge and decreasing size of ions (ionic charge densities increase).
• Hydration energies and lattice energies are usually of about the same magnitude for
low-charge species, so the dissolution process is slightly endothermic for many ionic
substances.
• As the charge-to-size ratio (charge density) increases for ions in ionic solids, the
magnitude of the crystal lattice energy usually increases more than the hydration
energy.
For example:
Aluminum fluoride, AlF3;
Magnesium oxide, MgO;
Chromium (III) oxide, Cr2O3 are very endothermic and not very soluble in water.
Dissolution of gases in liquids
The only gases that dissolve appreciably in water are:
Those that are capable of hydrogen bonding (such as HF)
Those that ionize (such as HCl, HBr, and HI)
Those that react with water (such as CO2).
Rate of dissolution and saturation
• The rate of dissolution, in contrast, is a measure of how fast a solute dissolves in a
solvent. There are three factors that affect the rate of dissolution: (1) the surface area
of the solute, (2) the temperature of the solvent, and (3) the amount of agitation that
occurs when the solute and the solvent are mixed.
• Dissolution and crystallization continue as long as excess solid is present, resulting in
a dynamic equilibrium analogous to the equilibrium that maintains the vapor pressure
of a liquid. We can represent these opposing processes as follows:
dissolution
Solute + Solvent Solution
crystallization
”
total concentration of solute species, regardless of their identities.
Description
Application
Performing calculations
Definition of Colligative properties
• Colligative properties are those properties of solution that depend only upon the total
concentration of solute species, regardless of their identities.
• These colligative properties include:
- vapor pressure lowering,
- boiling point elevation,
- freezing point depression,
- osmotic pressure.
This small set of properties is of central importance to many natural phenomena and technological
applications, as will be described in this presentation.
Vapor pressure lowering
As described in the chapter on liquids and solids, the equilibrium vapor pressure of a
liquid is the pressure exerted by its gaseous phase when vaporization and condensation
are occurring at equal rates:
liquid⇌gas
Where:
is the partial pressure exerted by component A in the solution,
is the vapor pressure of pure A,
is the mole fraction of A in the solution.
Recalling that the total pressure of a gaseous mixture is equal to the sum of partial
pressures for all its components (Dalton’s law of partial pressures), the total vapor pressure
exerted by a solution containing components is
Vapor pressure lowering and Raoult’s law
A nonvolatile substance is one whose vapor pressure is negligible ( P* ≈ 0), and so the
vapor pressure above a solution containing only nonvolatile solutes is due only to the
solvent:
Example
Calculation of a Vapor Pressure
Compute the vapor pressure of an ideal solution containing 92.1 g of glycerin, C3H5(OH)3,
and 184.4 g of ethanol, C2H5OH, at 40 °C. The vapor pressure of pure ethanol is 0.178 atm
at 40 °C. Glycerin is essentially nonvolatile at this temperature.
Example
Solution Since the solvent is the only volatile component of this solution, its vapor
pressure may be computed per Raoult’s law as:
First, calculate the molar amounts of each solution component using the provided mass
data.
Next, calculate the mole fraction of the solvent (ethanol) and use Raoult’s law to compute
the solution’s vapor pressure.
Distillation of Solutions
• Solutions whose components have significantly different vapor pressures may be
separated by a selective vaporization process known as distillation.
Consider the simple case of a mixture of two volatile liquids, A and B, with A being
the more volatile liquid. Raoult’s law can be used to show that the vapor above
the solution is enriched in component A, that is, the mole fraction of A in the vapor
is greater than the mole fraction of A in the liquid. By appropriately heating the
mixture, component A may be vaporized, condensed, and collected—effectively
separating it from component B.
• Distillation is widely applied in both laboratory and industrial settings, being used to
refine petroleum, to isolate fermentation products, and to purify water. A typical
apparatus for laboratory-scale distillations is shown in figure below.
A typical laboratory distillation unit is shown in (a) a photograph and (b) a schematic diagram
of the components. (credit a: modification of work by “Rifleman82”/Wikimedia commons;
credit b: modification of work by “Slashme”/Wikimedia Commons)
Oil refineries use large-scale fractional distillation to separate the components of crude oil.
The crude oil is heated to high temperatures at the base of a tall fractionating column,
vaporizing many of the components that rise within the column. As vaporized components
reach adequately cool zones during their ascent, they condense and are collected. The
collected liquids are simpler mixtures of hydrocarbons and other petroleum compounds
that are of appropriate composition for various applications (e.g., diesel fuel, kerosene,
gasoline), as depicted in the following figure.
Crude oil is a complex mixture that is separated by large-scale fractional distillation to isolate
various simpler mixtures.
Boiling Point Elevation
As described in the chapter on liquids and solids, the boiling point of a liquid is the
temperature at which its vapor pressure is equal to ambient atmospheric pressure.
Since the vapor pressure of a solution is lowered due to the presence of nonvolatile
solutes, it stands to reason that the solution’s boiling point will subsequently be
increased.
Vapor pressure increases with temperature, and so a solution will require a higher
temperature than will pure solvent to achieve any given vapor pressure, including one
equivalent to that of the surrounding atmosphere.
The increase in boiling point observed when nonvolatile solute is dissolved in a solvent,
Δ Tb, is called boiling point elevation and is directly proportional to the molal
concentration of solute species:
Step 2. Add the boiling point elevation to the pure solvent’s boiling point.
Freezing Point Depression
Solutions freeze at lower temperatures than pure liquids. This phenomenon is exploited in
“de-icing” schemes that use salt (Figure below), calcium chloride, or urea to melt ice on
roads and sidewalks, and in the use of ethylene glycol as an “antifreeze” in automobile
radiators. Seawater freezes at a lower temperature than fresh water, and so the Arctic and
Antarctic oceans remain unfrozen even at temperatures below 0 °C (as do the body fluids of
fish and other cold-blooded sea animals that live in these oceans).
where m is the molal concentration of the solute and Kf is called the freezing point
depression constant (or cryoscopic constant).
Just as for boiling point elevation constants, these are characteristic properties whose
values depend on the chemical identity of the solvent. Values of Kf for several solvents are
listed in the following table.
Freezing Point Depression
Step 2. Subtract the freezing point change observed from the pure solvent’s freezing point.
Freezing Point Depression
Freezing point depression is exploited to remove ice from (a) roadways and (b)
the control surfaces of aircraft.
Phase Diagram for a Solution
The colligative effects on vapor pressure, boiling point, and freezing point described in the
previous section are conveniently summarized by comparing the phase diagrams for a pure
liquid and a solution derived from that liquid.
Phase Diagram for a Solution
The osmotic pressure of a dilute solution is related to its solute molarity, M, and absolute temperature, T,
according to the equation
If a solution is placed in an apparatus like the one shown in the figure, applying pressure greater than the
osmotic pressure of the solution reverses the osmosis and pushes solvent molecules from the solution into the
pure solvent. This technique of reverse osmosis is used for large-scale desalination of seawater and on
smaller scales to produce high-purity tap water for drinking.
Osmosis and Osmotic Pressure of Solutions
Reverse osmosis systems for purifying drinking water are shown here on (a) small and
(b) large scales.
(credit a: modification of work by Jerry Kirkhart; credit b: modification of work by Willard
J. Lathrop)
Examples of osmosis system in biological systems
• Carrots and celery that have become limp because they have lost water can be made
crisp again by placing them in water. Water moves into the carrot or celery cells by
osmosis.
• A cucumber placed in a concentrated salt solution loses water by osmosis and
absorbs some salt to become a pickle.
• Osmosis can also affect animal cells. Solute concentrations are particularly important
when solutions are injected into the body. Solutes in body cell fluids and blood serum
give these solutions an osmotic pressure of approximately 7.7 atm. Solutions injected
into the body must have the same osmotic pressure as blood serum; that is, they
should be isotonic with blood serum. If a less concentrated solution,
a hypotonic solution, is injected in sufficient quantity to dilute the blood serum, water
from the diluted serum passes into the blood cells by osmosis, causing the cells to
expand and rupture. This process is called hemolysis. When a more concentrated
solution, a hypertonic solution, is injected, the cells lose water to the more
concentrated solution, shrivel, and possibly die in a process called crenation. These
effects are illustrated in the following figure.
Red blood cell membranes are water permeable and will (a) swell and possibly rupture
in a hypotonic solution; (b) maintain normal volume and shape in an isotonic solution;
and (c) shrivel and possibly die in a hypertonic solution. (credit a/b/c: modifications of
work by “LadyofHats”/Wikimedia commons)
Determination of Molar Masses
Osmotic pressure and changes in freezing point, boiling point, and vapor pressure are
directly proportional to the number of solute species present in a given amount of
solution. Consequently, measuring one of these properties for a solution prepared using
a known mass of solute permits determination of the solute’s molar mass.
Example
Determination of a Molar Mass from a Freezing Point Depression
A solution of 4.00 g of a nonelectrolyte dissolved in 55.0 g of benzene is found to freeze at
2.32 °C. Assuming ideal solution behavior, what is the molar mass of this compound?
Example
Solve this problem using the following steps.
Example
Step 1. Determine the change in freezing point from the observed freezing point and the freezing
point of pure benzene
Step 2. Determine the molal concentration from Kf, the freezing point depression constant for
benzene, and ΔTf.
Step 3. Determine the number of moles of compound in the solution from the molal concentration
and the mass of solvent used to make the solution.
Step 4. Determine the molar mass from the mass of the solute and the number of moles in that
mass.
Example
Determination of a Molar Mass from Osmotic Pressure
A 0.500 L sample of an aqueous solution containing 10.0 g of hemoglobin has an osmotic
pressure of 5.9 torr at 22 °C. Assuming ideal solution behavior, what is the molar mass of
hemoglobin?
Example
Here is one set of steps that can be used to solve the problem:
Step 1. Convert the osmotic pressure to atmospheres, then determine the molar concentration from
the osmotic pressure.
Step 2. Determine the number of moles of hemoglobin in the solution from the concentration and
the volume of the solution.
Step 3. Determine the molar mass from the mass of hemoglobin and the number of moles in that
mass.
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