Analytical Chrmistry
Analytical Chrmistry
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CC 102 – QUALITATIVE AND QUANTITATIVE CHEMISTRY
College of Liberal Arts, Sciences and Education
Prepared by: DENNIS M. DIMARANAN
ERWIN R. ABRENCILLO, PhD
particles remove some of the solvent molecules in the liquid phase. This also results in the reduction of the
concentration of the solvent.
Meanwhile, when we talk about the given solute-solvent mass ratio, colligative properties are said to be
inversely proportional to the solute molar mass.
If P0 is the vapour pressure of pure solvent and Ps is the vapour pressure of the solution. The difference Po – Ps
is termed as lowering in vapour pressure. The ratio Po – Ps / Po is known as the relative lowering of vapour
pressure.
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CC 102 – QUALITATIVE AND QUANTITATIVE CHEMISTRY
College of Liberal Arts, Sciences and Education
Prepared by: DENNIS M. DIMARANAN
ERWIN R. ABRENCILLO, PhD
Raoult, in 1886, established a relation between relative lowering in vapour pressure and mole fraction. The
relationship is known as Raoult’s law. It states that the relative lowering in vapour pressure of a dilute solution
is equal to the mole fraction of the solute present in the solution
If n moles of solute is dissolved in N moles of the solvent, then according to Raoult’s law
Po – Ps / Po = n / n + N
SAMPLE PROBLEM
Hexane and heptane were mixed to form an ideal solution. At 1000C, the vapour pressure of two liquids( Hexane
and heptane) are 190kPa and 45kPa respectively. What will be the vapour pressure of the solution obtained by
mixing 25g of hexane and 35 g of heptane will be:
Solution :
No of moles of hexane,n1= 25/86= 0.29
No of moles of heptane, n2=35/100=0.35
𝜒1 = n1 / n1 + n2
𝜒1 = 0.29 / 0.29 +0.35
𝜒1 = 0.45
𝜒2 = 1 – 0.45
𝜒2 = 0.55
P = P01𝜒1 +P02𝜒2
= 1900.45 + 450.55
=110 kPa
∆Tb ∝ m
∆Tb = kb m
Where,
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CC 102 – QUALITATIVE AND QUANTITATIVE CHEMISTRY
College of Liberal Arts, Sciences and Education
Prepared by: DENNIS M. DIMARANAN
ERWIN R. ABRENCILLO, PhD
kb = molal elevation constant
Substituting the value of ‘m’ in the above relation we get
∆Tb = 1000 x kb x m2 / M2 x m1
Where,
m2 = mass of solvent in g
M1 = mass of solvent in kg
M2 = molar mass of solute
Sample Problem
The molal elevation constant for water is 0.513o C kg mol–. When 0.2mole of sugar is
dissolved in 250g of water, calculate the temperature at which the solution boils under
atmospheric pressure.
Solution:
The elevation in boiling point can be written as
∆Tb = moles of sugar x 1000 / weight of water in gram
∆Tb = 0.2 x 1000 / 250
∆Tb = 0.8
⇒ T0b-Tb = 0.8
For pure water, T0b =100oC
⇒ Tb= 0.8 + 100
=100.80 0C
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CC 102 – QUALITATIVE AND QUANTITATIVE CHEMISTRY
College of Liberal Arts, Sciences and Education
Prepared by: DENNIS M. DIMARANAN
ERWIN R. ABRENCILLO, PhD
3. Depression in Freezing Point
The freezing point of a substance may be defined as the temperaturre at which the vapour pressure of the
substance in its liquid phase is equal to its vapour pressure in the soolid phase. According to Raoult’s law when
a non-volatile solid is added to the solvent its vapour pressure decreases and now it would become equal to
that of solid solvent at a lower temperature. The difference between the freezing point of the pure solvent and
its solution is called depression in freezing point.
If T0f is the freezing point of the pure solvent and Tf is the freezing point when non-volatile solute is dissolved in
it then depression in freezing point is given as
4. Osmotic Pressure
When a semipermeable membrane is placed between a solution and solvent, it is observed
that solvent molecules enter the solution through the semipermeable membrane and the
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CC 102 – QUALITATIVE AND QUANTITATIVE CHEMISTRY
College of Liberal Arts, Sciences and Education
Prepared by: DENNIS M. DIMARANAN
ERWIN R. ABRENCILLO, PhD
volume of the solution increases. The semi-permeable membrane allows only solvent
molecules to pass through it but prevents the passage of bigger molecules like solute. This
phenomenon of the spontaneous flow of solvent molecules through a semipermeable
membrane from a pure solvent to a solution or from a dilute to a concentrated solution is
called osmosis.
The flow of solvent molecules through the semipermeable membrane can be stopped if some
extra pressure is applied from the solution side. This pressure that just stops the flow of
solvent is called osmotic pressure of the solution.
Osmotic pressure is a colligative property as it depends on the number of solute present and
not on the nature of the solute. Experimentally it was proved that osmotic pressure (⫪) is
directly proportional to molarity(C) and temperature(T).
Mathematically, ℼ = CRT where R is the gas constant.
⇒ ℼ = (n2/V) RT
Here, V is the volume of solution in litres and n2 is moles of solute
If m2 is the weight of solute and M2 molar mass of solute, then n2= m2/M2
ℼ = W2 RT / M2V
Thus by knowing the values of ℼ,w2, T and V we can calculate the molar mass of the solute.
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CC 102 – QUALITATIVE AND QUANTITATIVE CHEMISTRY
College of Liberal Arts, Sciences and Education
Prepared by: DENNIS M. DIMARANAN
ERWIN R. ABRENCILLO, PhD
SAMPLE PROBLEM
300 cm3 of an aqueous solution contains 1.56g of a polymer. The osmotic pressure of such solution at 270oC
is found to be 2.57 ✕ 10-3 bar. Calculate the molar mass of the polymer
Solution:
Weight of polymer( W2) = 1.56g
Osmotic pressure (⫪) = 2.57 ✕ 10-3 bar
volume (V) = 300 cm3 = 0.3L
M2 = W2 RT / ℼ V
= 1.56 x 0.083 x 300 / 0.3 x 2.57 x 10-3
= 50381 g mol–
Different Solutions
• Isotonic solution: Two solutions having the same osmotic pressure at a given
temperature are known as an isotonic solution. When such solutions are separated by a
semi-permeable membrane than there is no osmosis.
• Hypotonic solution: A hypotonic solution has a lower osmotic pressure than that of the
surrounding i.e, the concentration of solute particles is less than that of the surrounding.
If the hypotonic solution is separated by semipermeable membrane then water moves
out of the hypotonic solution.
• Hypertonic solution: A hypertonic solution has a higher osmotic pressure than that of the
surrounding i.e, the concentration of solute particles is more than that of the surrounding.
If the hypertonic solution is separated by semipermeable membrane then water moves
inside the hypertonic solution.
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CC 102 – QUALITATIVE AND QUANTITATIVE CHEMISTRY
College of Liberal Arts, Sciences and Education
Prepared by: DENNIS M. DIMARANAN
ERWIN R. ABRENCILLO, PhD
For determining the molar mass, Osmotic pressure method has the advantage over other
methods as pressure measurement is around room temperature. It is particularly useful for
determination of the molar mass of biomolecules as they are unstable at higher temperatures.
LEARNING TASKS
Solve the following problems
1. What is the vapor pressure of the pure solvent if the vapor pressure of a solution of 10 g
of sucrose (C6H12O6) in 100 g of ethanol (C2H6O) is 55 mmHg?
2. A solution is made by mixing 12.0 g of C10H8 in 45.0 g of C6H6. If the vapour pressure
of pure C6H6 is 95.3 torr, what is the vapour pressure of the solution?
3. What is the boiling point of a 2.50 m solution of C6H4Cl2 in CCl4? Assume that C6H4Cl2 is not
volatile.
4. What is the freezing point of a 1.77 m solution of CBr4 in C6H6?
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CC 102 – QUALITATIVE AND QUANTITATIVE CHEMISTRY
College of Liberal Arts, Sciences and Education
Prepared by: DENNIS M. DIMARANAN
ERWIN R. ABRENCILLO, PhD
5. solution is made by mixing 12.0 g of C10H8 in 45.0 g of C6H6. If the vapour pressure of
pure C6H6 is 76.5 torr at a particular temperature, what is the vapour pressure of the
solution at the same temperature?
6. A solution is made by mixing 43.9 g of C6H12C6 in 100.0 g of H2O. If the vapour pressure
of pure water is 26.5 torr at a particular temperature, what is the vapour pressure of the
solution at the same temperature?
7. At 300°C, the vapour pressure of Hg is 32.97 torr. If 0.775 g of Au were dissolved into
3.77 g of Hg, what would be the vapour pressure of the solution?
8. At 300°C, the vapour pressure of Hg is 32.97 torr. What mass of Au would have to be
dissolved in 5.00 g of Hg to lower its vapour pressure to 25.00 torr?
9. If 25.0 g of C6H12O6 are dissolved in 100.0 g of H2O, what is the boiling point of this
solution?
References:
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