CHM012

Chemistry  for  
Engineers
Topic 7:
Properties of Solutions

Tel.   | Page
 Solutions
❖ Solutions  are  homogeneous   mixtures  of   two  or  more  pure   substances.
❖ In  a  solution,   the  solute is  dispersed   uniformly   throughout   the  solvent.
❖ The  ability  of  substances  to  form   solutions   depends   on
natural  tendency  toward  mixing.
intermolecular   forces.

Properties  of  a  True  Solutions

1. A  homogeneous   mixture  of  2  or  more  components   whose  ratio  can  be  varied.
2. The  dissolved   solute   is  molecular  or  ionic  in  size  (less  than  1  nm).
3. Liquid   or  gaseous   solutions   can  be  colored  or  colorless  and  are  usually  transparent.
4. The  solute   will  not  settle  out   of  the  solution.
5. The  solute   can  be  separated  from   the  solvent   by  physical  means.

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 Natural  Tendency  toward  Mixing
❖ Mixing   of  gases  is  a  spontaneous process.
❖ Each  gas  acts  as  if  it  is  alone  to  fill  the  container.
❖ Mixing   causes  more   randomness   in  the  position   of  the  molecules,  increasing   a  thermodynamic   quantity   called  
entropy.
❖ The  formation   of  solutions   is  favored  by  the  increase  in  entropy   that  accompanies  mixing.

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 Intermolecular  Forces  of  Attraction
Any  intermolecular   force  of  attraction  can  be  the  attraction  between  solute   and  solvent   molecules.

✔ Solute–solute   interactions must  be  overcome   to  disperse  these  particles  when  making  a  solution.
✔ Solvent–solvent   interactions must  be  overcome   to  make  room   for  the  solute.
✔ Solvent–solute   interactions occur  as  the  particles  mix.

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 Energetics  of  Solution  Formation
Cardinal  rule  of  solubility   is  “like  dissolves  like”
✔ A  polar  solvent  must  be  used  to  dissolve   a  polar  or  ionic  solute
✔ A  nonpolar   solvent   must  be  used  to  dissolve  a  nonpolar   solute

1.    Solute  particles   separate  from  each  other -­‐ endothermic

solute  (aggregated)   +  heat à solute  (separated)              ΔHsolute >  0

2.    Solvent  particles   separate  from  each  other -­‐ endothermic

solvent  (aggregated)   +  heat à solvent  (separated)              ΔHsolvent >  0

3.    Solute  and  solvent  particles  mix  – always exothermic

solute  (separated)   +  solvent  (separated)        à solution   +  heat   ΔHmix <  0

ΔHsoln =  ΔHsolute +  ΔHsolvent +  ΔHmix

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 Energetics  of  Solution  Formation

Exothermic  solution  process Endothermic  solution  process

△Hmix is  larger  than  the  sum  o f  △Hsolute and  △Hsolvent,   △Hmix is  smaller  than  the  sum  o f  △Hsolute and  △Hsolvent,  
so  △Hsoln is  negative so  △Hsoln is  positive

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 Energy  Terms  for  Various  Types  of  Solutes  and  
Solvents
ΔHsolute ΔHsolvent ΔHmix ΔHsoln Outcome
Polar  solute,  polar  solvent Large Large Large,  negative Small Solution  forms

Nonpolar  solute,  polar   Small Large Small Large,  positive No  solution  

solvent forms
Nonpolar  solute,  nonpolar   Small Small Small Small Solution  forms
solvent
Polar  solute,  nonpolar   Large Small Small Large,  positive No  solution  
solvent forms

In  case  of  polar–polar   and  nonpolar–nonpolar,   the  heat  of  solution   is  expected  to  be  small
✔ Solution   forms  because  of  the  increase  in  the  probability   of  the  mixed  state
In  the  other  cases  (polar–nonpolar   and  nonpolar–polar),   the  heat  of  solution   is  expected  to  be  large  and  positive
✔ Large  quantity   of  energy  required   acts  to  prevent  the  solution   from   forming
Helps  in  understanding   the  observations   that  like  dissolves   like

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 Example
Decide  whether  liquid   hexane  (C6H14)   or  liquid   methanol  (CH3OH)   is  the  more   appropriate   solvent  for  the  substances  
grease  (C20H42)  and  potassium   iodide  (KI)

Grease

Potassium
Iodide

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Solubility

ü The solubility (S) of a solute is the maximum amount that dissolves in a fixed quantity of a given
solvent at a given temperature, when an excess of the solute is present.

Different solutes have different solubilities:

• Sodium chloride (NaCl), S 5 39.12 g/100. mL water at 100.8 C
• Silver chloride (AgCl), S 5 0.0021 g/100. mL water at 100.8 C

ü Solubility is a quantitative term, but dilute and concentrated are qualitative, referring to the
relative amounts of dissolved solute;
v the NaCl solution above is concentrated, and the AgCl solution is dilute.

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Solubility

• Saturated solution -­‐ at equilibrium and contains the maximum

amount of dissolved solute at a given temperature in the presence of
undissolved solute. Therefore, if you filter off the solution and add
more solute, it doesn’t dissolve.

• Unsaturated solution -­‐ contains less than the equilibrium

concentration of dissolved solute; add more solute, and more
dissolves until the solution is saturated.

• Supersaturated solution -­‐ contains more than the equilibrium

concentration and is unstable relative to the saturated solution.

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 Factors  that  Affects  Solubility
✔ Solute–solvent  Interactions  (Structure   Effect)
✔ Pressure  (for   gaseous   solutes)
✔ Temperature

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 Solute-­Solvent  Interaction
❖ Molecular  structure  determines  polarity  -­‐ If  the  solute  and  solvent  have  similar  polarities,  solubility  is  
favored.  
✔ Nonpolar  substances  are  described  as  hydrophobic  (water-­‐fearing).  Example  -­‐ Vitamin  A
✔ Polar  substances  are  described  as  hydrophilic  (water-­‐loving).  Example  -­‐ Vitamin  C
❖ The  stronger the  solute–solvent  interaction,  the  greater the  solubility  of  a  solute  in  that  solvent.

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 Pressure  Effects
❖ The  solubility   of  solids  and  liquids   are  not appreciably  affected  by  pressure.
❖ Gas  solubility   is  affected  by  pressure.

✔ Henry’s  Law  -­‐ The  solubility   of  a  gas  is  proportional   to  the  partial  pressure  
of  the  gas  above  the  solution.

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 Temperature  Effects
✔ For most solids, as temperature increases, solubility
increases. However, clearly this is not always true—some
increase greatly, some remain relatively constant, and
others decrease.
✔ For all gases, as temperature increases, solubility
decreases. Cold rivers have higher oxygen content than
warm rivers.

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 Solution  Concentrations
Mass  percentage  (%)

Parts  per  million   (ppm)

Parts  per  billion   (ppb)

Mole  fraction  (X)

Molarity  (M)

Molality  (m)

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 Example
A  solution   is  prepared   by  mixing  1.00  g  ethanol  (C2H5OH)   with  100.0  g  water  to  give  a  final  volume   of  101  mL.  Calculate  
the  molarity,  mass  percent,  mole  fraction,   and  molality  of  ethanol  in  this  solution.

Solution

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 Example
Electrolyte  in  automobile   lead  storage  batteries  is  a  3.75  M  sulfuric   acid  solution   that  has  a  density  of  1.230  g/mL.  
Calculate  the  mass  percent  and  molality  of  the  sulfuric   acid.

Solution

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 Example
Certain soft drink is bottled so that at 25°C, it contains CO2 gas at a pressure of 5.0 atm over the liquid. Assuming that
the partial pressure of CO2 in the atmosphere is 4.0×10–4 atm, calculate the equilibrium concentrations of CO2 in the
soda both before and after the bottle is opened. Henry’s law constant for CO2 in aqueous solution is 3.1×10–2
mol/L·∙atm at 25°C.

Solution

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 Colligative  Properties
✔ Colligative  property  – is  a  property  of  a  solution  that  depends  only  on  the  quantity of  solute,  NOT on  
the  identity of  the  solute  particles.

❖ Among  colligative  properties  are:

Vapor  pressure  lowering  – the  vapor  pressure  of  the  solution  is  lower  than  the  pure  solvent.
Boiling-­‐point  elevation  – the  boiling  point  of  the  solution  is  higher  than  the  pure  solvent.
Freezing-­‐point  depression  – the  freezing  point  of  the  solution  is  lower  than  the  pure  solvent.
Osmotic  pressure  – is  the  pressure  applied  to  prevent  osmosis.

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 Vapor  Pressure  Lowering
Because of solute–solvent intermolecular attraction, higher concentrations of nonvolatile solutes make it harder for
solvent to escape to the vapor phase. Therefore, the vapor pressure of a solution is lower than that of the pure
solvent.

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 Raoult  s  Law
‘
✔ The vapor pressure of a volatile solvent over the solution is
the product of the mole fraction of the solvent times the
vapor pressure of the pure solvent.

Psoln =  Observed  vapor  pressure   of  solution

χsolv =  Mole  fraction   of  solvent
P°solv =  Vapor  pressure   of  pure  solvent  

• In ideal solutions, it is assumed that each substance will follow

Raoult’s Law.

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 Example
Calculate the expected vapor pressure at 25°C for a solution prepared by dissolving 158.0 g common table sugar
(sucrose, molar mass = 342.3 g/mol) in 643.5 cm3 of water. At 25°C, the density of water is 0.9971 g/cm 3 and the vapor
pressure is 23.76 torr.

Solution

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 Example
Predict  the  vapor  pressure  of  a  solution   prepared  by  mixing   35.0  g  solid   Na2SO4 (molar   mass  =  142.05  g/mol)   with  175  
g  water  at  25°C.  Vapor  pressure   of  pure  water  at  25°C  is  23.76  torr.  

Solution

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 Non-­ideal  Solutions
For  liquid–liquid   solutions   where  both   components   are  volatile,   a  modified   Raoult’s  law  applies

• PTOTAL =  total  vapor  pressure  of   a  solution   containing   A  and  B

• χA and  χB =  mole  fractions  of  A  and  B
• PA° and  PB° =  vapor   pressures  of  pure   A  and  pure  B
• PA and  PB =  partial  pressures  of  A  and  of  B  in  the  vapor  above  the  solution

Note:
✔ When a solute and solvent release large quantities of energy (exothermic) in the formation of a solution, that is,
when ΔHsoln is large and negative. We expect a negative deviation from Raoult’s law.
✔ If two liquids mix endothermically, it indicates that the solute–solvent interactions are weaker than the
interactions among the molecules in the pure liquids, positive deviations from Raoult’s law are observed.
✔ For a solution of very similar liquids, the enthalpy of solution is very close to zero, and thus the solution closely
obeys Raoult’s law (ideal behavior)

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 Vapor  Pressure  for  a  Solution  of  Two  Volatile  Liquids
Interactive  Forces  Between   ΔT  for  
Deviation  from  
Solute  (A)  and  Solvent  (B)   ΔHsoln Solution   Example
Raoult’s  Law
Particles Formation
A  ↔  A,  B  ↔  B  ≡  A  ↔  B Zero Zero None  (ideal  solution)   Benzene–toluene
A  ↔  A,  B  ↔  B  ˂  A  ↔  B Negative  (exothermic) Positive Negative Acetone–water
A  ↔  A,  B  ↔  B  >  A  ↔  B Positive  (endothermic) Negative Positive Ethanol–hexane

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 Concept  Check
For  each  of  the  following   solutions,   would  you  expect  it  to  be  relatively  ideal  (with  respect  to  Raoult’s Law),  show  a  
positive   deviation,   or  show  a  negative  deviation?
a. Hexane  (C6H14)   and  chloroform   (CHCl3)  à
b. Ethyl  alcohol  (C2H5OH)  and  water  à
c. Hexane  (C6H14)   and  octane  (C8H18)  à

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 Example
A solution is prepared by mixing 5.81 g acetone (C3H 6O, molar mass = 58.1 g/mol) and 11.9 g chloroform (HCCl3, molar
mass = 119.4 g/mol). At 35°C, this solution has a total vapor pressure of 260 torr. Determine if this is an ideal solution.
Vapor pressures of pure acetone and pure chloroform at 35°C are 345 and 293 torr, respectively.

Solution

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 Boiling  Point  Elevation

❖ Since  vapor  pressures  are  

lowered  for  solutions,  it  
requires  a  higher  
temperature  to  reach  
atmospheric  pressure.  
Hence,  boiling  point  is  
raised.

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 Freezing  Point  Depression

❖ The  construction  of  the  phase  

diagram  for  a  solution  
demonstrates  that  the  freezing  
point  is  lowered  while  the  
boiling  point  is  raised.

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 Boiling-­Point  Elevation  and  Freezing-­Point  Depression
The  change  in  temperature   is  directly  proportional   to  molality  (using   the  van’t  Hoff   factor).

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 The  van  t  Hoff  Factor  (i  )
‘
It  takes  into  account  dissociation   of  solutes  in  solution.
Theoretically,  we  get  2  particles  when  NaCl  dissociates.  So,  i =  2.
In  fact,  the  amount   that  particles  remain  together   is  dependent   on  the  concentration   of  the  solution.

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 Example
A  solution   prepared   by  dissolving   18.00  g  glucose  in  150  g  water  has  a  boiling   point   of  100.34°C.  Calculate  the  molar  
mass  of  glucose.  Glucose  is  a  molecular   solid  that  is  present  as  individual   molecules  in  solution.
Solution

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 Example
Determine the mass of ethylene glycol (C2H6O2 , molar mass = 62.1 g/mol), the main component of antifreeze, to be
added to 10.0 L of water to produce a solution for use in a car’s radiator that freezes at –10.0°F (–23.3°C). Assume the
density of water is exactly 1 g/mL.

Solution

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 Example
A chemist is trying to identify a human hormone that controls metabolism by determining its molar mass. A sample
weighing 0.546 g was dissolved in 15.0 g benzene, and the freezing-­‐point depression was determined to be 0.240°C.
Calculate the molar mass of the hormone.

Solution

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 Osmosis
Some  substances  form   semipermeable  membranes,  allowing   some  smaller  particles  to  pass  through,   but  blocking  
larger  particles.
The  net  movement   of  solvent   molecules  from   solution   of  low  to  high   concentration   across  a  semipermeable  
membrane   is  osmosis.  The  applied  pressure   to  stop   it  is  osmotic  pressure.

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 Osmotic  Pressure
❖ Osmotic  pressure  is  a  colligative  property.

∏  =  Osmotic  pressure   (atm)

M =  Molarity  of  the  solution
R =  Ideal  gas  constant
T =  Temperature  (Kelvin)

❖ If  two  solutions   separated  by  a  semipermeable   membrane   have  the  same osmotic  pressure,   no  osmosis  
will  occur.

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 Example
To determine the molar mass of a certain protein, 1.00x10–3 g of it was dissolved in enough water to make 1.00 mL of
solution. Osmotic pressure of the solution was found to be 1.12 torr at 25.0°C. Calculate the molar mass of the protein.

Solution

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