Solutions
By Jason DoubA solution is defined as a
homogeneous mixture or a mixture where the components are uniformly mingled. Normally we
thing of a solution is the liquid state, but this is a common misconception; a solution
can be in any state. For example, air is a solution of oxygen, nitrogen, and a variety of
other gases all in the gas state. Steel is also solution of carbon and iron, but this
solution exists in the solid state. However, the most important solutions in chemistry
involve water, so this section will focus of aqueous solution.
Before we begin discussing the properties of solutions, we must define ways to describe
the concentrations of various mixtures:
Molarity (M): the number of moles per liter (moles/Liter)
Mole fraction (c ): the ratio of the number of moles
of a compound to the number of moles of solution (c A = moles A
/ (Moles A + Moles B))
Molality (m): the number of moles solute1 per kilogram solvent
(m = moles solute/ kilograms solvent)
Mass percent or weight percent: the percent by mass of a solute1
in a solution (Mass percent = mass solute / mass solution * 100)
1
A solute is the compound being dissolved in medium. The solvent
is the medium in which the compound in being dissolved.
Forming a solution
Dissolving compound in liquids, such as water, is very common; so it would be
valuable to understand how and why compound form solutions. To address these questions we
must examine what happens when you add a compound to a liquid:
Step 1
: the solute particles separate (overcoming the
intermolecular attractive forces).
Step 2
: the solvent particles separate (overcoming the
intermolecular attractive forces).
Step 3
: the solute and solvent interact to form the
solution.
Each of these steps results in a change of energy. We can sum these energy changes to
find the energy change of the solution, called enthalpy (heat) of
solution (D Hsoln). Therefore, the D Hsoln is:
D Hsoln = D
H1 + D H2 + D H3
The first two steps usually result in a large positive D
H, but the third step is usually negative. If the first two enthalpies are greater that
the third, the overall D Hsoln will be positive and
vice versa. It is important to note, that process with a large positive D Hsoln tend not to occur; however, process with small
positive D Hsoln may occur because nature strives
for disorder (entropy), and a solution is more disordered than its individual components.
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The above concepts can be applied to understand structure can effect solubility;
lets use water mixed with oil for an example. The first two steps from above result
in a positive D H, because it requires energy to break
waters hydrogen bonding, and oils dispersion forces. The third step does not
counter this with a large negative D H, because there is little
interaction between oil and water. Thus the D Hsoln
is large and positive, so the reaction is not favored. Salts do dissolve in water, because
they have a significant interaction with water resulting in a low D
Hsoln. Salts are describes as hydrophilic (water loving) where oils are
called hydrophobic (water fearing).
Pressure can also effect the solubility of gasses; the relationship between pressure
and the concentration of dissolved gas is described in Henrys law; the amount of gas
dissolved is directly proportional to the pressure of the gas above the solution:
P=kC
Temperature effects the solubility of solutions. One normally thinks that by heating
the solution, more solute can be dissolved: this is a misconception. There is come
correlation between D Hosoln of a
solution and the solubility (see Le Chateliers Principle), but the temperature
dependence can only truly be seen by experiments.
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Gases dissolved in a solution follow a simple rule; the higher the temperature, the
less gas dissolved.
Effects of solutions
When a nonvolatile solute is added to a solvent, the vapor pressure of the solvent
is lowered. Fancois M. Raoult studied phenomenon, and his results are desribes by Raoults
Law:
Psoln = C solventPosolvent
One is able to use a simple model to understand the phenomenon; think of the
dissolved solute molecules evenly distributed in the solution, even at the surface. Then
understand that this caused less molecules of volatile solvent to be at the surface and
less molecules evaporating.
This decrease in vapor pressure as a result of the solution can help to explain the
following colligative properties, properties that depend only on the number
of molecules not he molecules themselves.
When a nonvolatile solute is added to a solvent, the boiling point of the solution is higher
than that of the pure solvent. This can be explained by the decreased vapor pressure of
the solution; the solution boils when the vapor pressure matches the outer pressure
(usually 1 atm), but since the vapor pressure is lowered, a higher temperature is needed
to match that outer pressure. This change is given by the equation:
D T = Kbmsolute
Similarly, when a nonvolatile solute is added to a solvent, the freezing point of
the solution is lower than that of the pure solvent. This is also explained by the
decreased vapor pressure; the solution freezes when the vapor pressure for the liquid and
solid phases is the same. This occurs at a lower temperature because of the decreased
vapor pressure. This change is given by the equation;
D T = Kfmsolute
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The osmotic pressure of a solution is also a colligative property. Osmotic
pressure (p ) is the pressure that must be applied to stop
osmosis, or the flow of solvent down a concentration gradient. The solvent attempts to
move to an area where there is a lesser concentration; the driving force of this movement
is an increase in disorder. Experimentally, the osmotic pressure has been show to follow
the equation:
p = MRT
where p is the osmotic pressure in atmospheres, M is the
molarity of the solute, R is the universal gas law constant, and T is the temperature.
All these colligative properties must be slightly changed for electrolytes, which
breakup into multiple pieces. The vant Hoff factor i must be inserted
into the equations. The vant Hoff factor I is:
i = moles of particle in solution / moles of solute dissolved
Therefore, the new modified freezing point and boiling point equation is:
D T = iKm
The modifies osmotic pressure equation is:
p = iMRT
One should note that ion pairing may result is slightly lowered results than
calculated. For example I for NaCl is 2, but the observed i for a .10 m
solution is 1.87. This is caused by a few ions pairing together making a fewer number of
molecules.
Colloids
A colloid is similar to a solution, except that a colloid is a suspension of
single large molecule or clumps of small molecules. Mud is an example of a colloid; the
mud particles stick together and remain suspended in water for an extremely long period of
time. The reason these particles remain in solution is that they have layers of oppositely
charged articles. When the charges on the outside of these particles are the same, they
experience electrostatic repulsion and remain suspended.
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Colloids can be destroyed, called coagulation, by heating or adding an electrolyte.