Chapter-3

Solution: Various types of standard solution; Preparation

of standard solution; Titrimetry; Nernst distribution law;
Deviations from distribution laws; Solvent extraction;
Properties of non-volatile, non-electrolytic dilute
solutions; Raoult’s law of vapour pressure lowering;
Elevation of boiling point and depression of freezing
point; Vant Hoff’s law of osmotic pressure;
Determination of molecular weight of substances using
Raoult’s law; Application of Vant Hoff’s law for measuring
molecular weight of monomers and polymers;
Determination of molecular weight of gases and volatile
liquids using ideal gas equation.

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 Solution
A solution is a homogenous mixture of two or more substances.
The substance present in the largest amount (moles) is referred to as the solvent.
The other substances present are called the solutes.
A substance that dissolves in a particular solvent is said to be soluble in that solvent.

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Various types of standard solution
Standard solutions:
A solution whose concentration is accurately
known is called a standard solution.
There are two types of standard solutions:
1. Primary standard solution
2. Secondary standard solution

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 Primary standard solution
Primary standard solutions are prepared from primary standard
substances. A primary standard substance is a substance of high
purity (99.9% pure) which may be dissolved in a known volume of
solvent to give a primary standard solution.

Primary standards have special chemical and physical properties.

These compounds are extremely pure and highly stable. Therefore,
we can obtain pure solutions using these compounds.

For example, if we want to prepare a standard solution of 0.1molL-1

concentration, we can calculate the weight of the primary standard
required for this and then dissolve that amount in a suitable solvent.
This gives exactly the 0.1 molL-1 solution with a high purity.

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 Secondary standard solution
Secondary standard solution is prepared from a secondary standard
substance.

Secondary standard solutions are usually used to calibrate analytical

equipment and analytical techniques. These solutions do not fulfill the
requirements of a primary standard.
A secondary standard substance has a less purity than a primary
standard. These are less stable and chemically reactive than primary
standards. Therefore, these compounds can get contaminated.

For example, anhydrous sodium hydroxide is a secondary standard. It is

highly hygroscopic. Potassium permanganate is another compound that
is often used as a secondary standard. It is less stable and is reactive.
Therefore, when a potassium permanganate solution is being prepared,
it has to be standardized with a primary standard.

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 Preparation of a standard solution by
weighing method
A standard solution can be prepared by weighing
method in the following way.
(a) The mass of solute needed is calculated and
weighed.
(b) The solute is dissolved in some distilled water in a
beaker.
(c) The solution is transferred into a volumetric flask.
(d) More distilled water is added to obtain the required
volume. The flask is stoppered and shaken.
For example, to prepare 1.0 dm3 of 0.50 mol dm-3
aqueous sodium hydroxide.

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 Preparation of 1.0 dm3 of 0.50 mol dm-3
aqueous sodium hydroxide

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Dilution is the procedure for preparing a less concentrated
solution from a more concentrated solution.

Dilution
Add Solvent

Moles of solute Moles of solute

before dilution (i) = after dilution (f)

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MiVi =
Chapter - 3
MfVf
12
4.5
 How would you prepare 60.0 mL of 0.2 M
HNO3 from a stock solution of 4.00 M HNO3?

MiVi = MfVf

Mi = 4.00 Mf = 0.200 Vf = 0.06 L Vi = ? L

MfVf 0.200 x 0.06

Vi = = = 0.003 L = 3 mL
Mi 4.00

3 mL of acid + 57 mL of water = 60 mL of solution

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 Titration

Titration:
Titration is an analytical NaOH Solution
method in which a standard
solution is used to determine
the concentration of an
standard Acid solution
unknown solution.

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unknown solution15
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 Titration
• Equivalence point (endpoint)
– Point at which equal amounts
of H3O+ and OH- have been
added.
– Determined by…
• indicator color change

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 Acid-Base Titration

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 Titration
Curve

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 Nernst's distribution law
Distribution law or the Nernst's distribution law gives a
generalization which governs the distribution of a solute
between two immiscible solvents.
• The distribution law states that a solute gets
distributed between the two layers of immiscible
solvents in such a way that the ratio of its
concentration in each solvent becomes equal to the
ratio of its solubility. C1/C2 = KD
• where c1 and c2 are the molar equilibrium
concentrations, the constant KD is the distribution
coefficient.

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 Nernst's distribution law
(Kinetic Theory)
If two immiscible solvents A and B are taken in a
separating funnel, they form two separate layers.
When a solute X which is soluble in both solvents is
added, it gets distributed or partitioned between
them. Molecules of X pass from solvent A to B and
from solvent B to A. Finally a dynamic equilibrium is
set up. At equilibrium, the rate, at which molecules
of X pass from one solvent to the other is balanced.
Cont..

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 Nernst's distribution law
Conc. of X in Solvent A= Conc. of X in Solvent B
At equilibrium, k1C1= k2C2
C1/C2 = k2/k1 = KD
Where k1 and k2 are the rate constants and C1
and C2 are the concentration of the solute in the
two phases.

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 Nernst's distribution law

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 Nernst's distribution law

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 Nernst's distribution law
In general it has been found that when a solute is shaken up with
two solvents which are immiscible with each other, but in both
of which the solute is soluble, then the solute distributes itself
between the two solvents in such a that the ratio of the
concentrations of the solute in the two solvents are constant at
constant temperature, provided the solute is in the same
molecular condition in the two liquids. This statement of what is
known as Nernst's distribution law.
If C1 and C2 are the concentrations of the solute in solvent 1 and
solvent 2 respectively, then according to this law,
C1/C2 = KD = constant
The constant KD is known as the distribution coefficient or
partition coefficient.

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 Applications of Distribution law
The distribution law can be applied to a number of
physical and chemical processes. Some of which are
mentioned below:
• The most important application of distribution law is
in the solvent extraction ( i.e. extraction of a solute
from a solvent by another solvent).
• Solubility of a solute can be measured by this law
• It is used in high performance liquid chromatography
(HPLC)
• It may also be used to determine the degree of
dissociation of acids, bases or salts in a solvent.
• The law can be applied to determine the equilibrium
constant of the reaction, KI + I2 KI3

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 Deviations from distribution laws
In several cases, the deviation of distribution law
has been observed and there is a systematic
increase or decrease in the value of distribution
coefficient (KD) with change in concentration of the
solute. Such deviations have been explained on the
basis of molecular association/dissociation or
complex formation of the solute in the solution.
If the solute undergoes association/dissociation
/complex formation in one of the solvents but
remains unchanged in the other, the law cannot be
applied.

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 Solvent Extraction
Solvent extraction is the process in which a compound
transfers from one solvent to another owing to the
difference in solubility or distribution coefficient
between these two immiscible (or slightly soluble)
solvents.

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 Calculation for the mass of solute
remaining after solvent extraction
Let w g of solute be in solution in v mL of solvent
I and this is extracted with I mL of solvent II,
which is immiscible with solvent I. If w1 g of
solute remains in solvent I after first extraction
(w – w1) g of the solute would be extracted by
solvent II. The concentrations (g/mL) of the
solute in solvent I and solvent II are respectively
w1/v and (w – w1)/I. The distribution co-efficent,
KD, is then given by

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 Solving for w1 one obtains

After the second extraction with fresh I mL of

solvent II, let w2 g of the solute remain in
solvent I; then

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 Solving for w2 one obtains
2
KDv KDv
w2 = w1 =w
KDv+1 KDv+1

If the extraction is repeated n number of times with l mL of

solvent II at each step the mass of solute wn, remaining in
solvent I after n extraction is given by,

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 Problems
Example 8.7: The solubility of methylamine at 18C in
water is 8.49 times greater than that in chloroform. What
percentage at the substance remains in 1000 mL of
chloroform solution of methylamine if it is extracted (a)
four times with 200 mL of water each time and (b) twice
with 400 mL of water each time?

Problems #1: The solubility of ethylamine at 25C in

water is 5.50 times greater than that in chloroform. What
percentage at the substance remains in 1000 mL of
chloroform solution of ethylamine if it is extracted (a)
eight times with 100 mL of water each time and (b) four
times with 200 mL of water each time?
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 Solution : For solvent extraction, we know

wn = w KDv n
KDv+1

So for (a)

4
(1/8.49 x 1
w4 = 100
(1/8.49) x 1 + 0.2

= 100  1.0189

= 1.89 %

Where, the volumes have been expressed in litres and w shown as 100 for expressing in per cent.

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 For (b)

2
(1/8.49 x 1
w2 = 100
(1/8.49) x 1 + 0.4

= 100  0.0517

= 1.17 %

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 Problems #2
The partition co-efficient of iodine between CS2 and water, KD = Corg/Cwater is 410,
at 25C. A solution containing 8 g of KI L-1 (0.0482 mol L-1) was shaken with
iodine and CS2 till equilibrium was established. The concentration of iodine in the
aqueous and organic layers were found to be 8.46  10-3 mol L-1 and 13.910-2 mol
L-1 respectively. Calculate the equilibrium constant of the reaction KI + I2 KI3.
[MW of KI = 39. 1+126.9 =166.0]

Problems #3
The distribution co-efficient of H2S between benzene and water, KD = Cb/Cw is 6.0
at 25C. Calculate the minimum volume of benzene necessary at this temperature
to extract in a single step 80% of the H2S from 0.5 L of a 0.1 mol L-1 aqueous
solution of H2S.

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Dilute solutions containing non-volatile solute
exhibit the following properties :
(1) Lowering of the Vapour Pressure
(2) Elevation of the Boiling Point
(3) Depression of the Freezing Point
(4) Osmotic Pressure

These four properties of solutions are intimately connected to each

other that they are grouped together and are commonly known as the
‘colligative properties’.

All the four properties depend only on the number of molecule in the
solution but they are independent of molecular structure.

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 Lowering of the Vapour Pressure
F M Raoult (1887-1888) stated that the relative
lowering of vapour pressure of a solvent due to
the addition of non-volatile, non-electrolyte
solute is equal to the mole fraction of the solute
in solution. This statement is known as Raoult’s
law.

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 Mathematical Expression of Raoult’s
Law
If p0 and p are the vapour pressure of the pure
solvent and solution respectively, then the relative
lowering of vapour pressure is (p0 –p)/p0
In a solution containing n moles of solute in N
moles of solvent, the mole fraction of solute is
n/(N+n). According to Raoult’s law,
(p0 –p)/p0 = n/(N+n) = x2 (mole fraction of solute)
The above equation can be written as follows:
1 - (p0 –p)/p0 =1- x2 = x1 (mole fraction of solvent)
Or, p = p0. x1 (mole fraction of solvent)

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 Vapor of solution is XwaterP0water = 0.9085x 17.5 mmHg = 15.90 mmHg

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Molar Mass of Non-volatile Solute
According to Raoult’s Law, (p0 –p)/p0 = n/(N+n)
n= No. of moles of solute & N = No. of moles of
solvent
For dilute solution, n is very small compared to N.
So, the above equation can be written as:
(p0 –p)/p0 = n/(N+n) = n/N
n= w/M ; where, w is the wt. of solute & M is the
molecular wt. of solute
N= w′/M′; where, w′ is the wt. of solvent & M′ is
the molecular wt. of solvent.
Thus we can write, (p0 –p)/p0 = n/N =wM′/Mw′

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 Elevation of Boiling Point
 The increase in boiling point observed when
nonvolatile solute is dissolved in a solvent, ΔTb, is
called boiling point elevation and is directly
proportional to the molal concentration of solute
species:
 ΔTb=Kbm
 where Kb is the boiling point elevation constant,
or the ebullioscopic constant and m is the molal
concentration (molality) of all solute species.

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Boiling point elevation constants are characteristic properties that
depend on the identity of the solvent.
Values of Kb for several solvents are listed in the following Table

Solvent Boiling Point Kb (Cm−1) Freezing Point Kf (Cm−1)

(°C at 1 atm) (°C at 1 atm)

water 100.0 0.512 0.0 1.86

hydrogen 118.1 3.07 16.6 3.9

acetate

benzene 80.1 2.53 5.5 5.12

chloroform 61.26 3.63 −63.5 4.68

nitrobenzene 210.9 5.24 5.67 8.1

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 Problem-1
What is the boiling point of a 0.33 m solution of
a nonvolatile solute in benzene?

Solution:
ΔTb=Kbm = 2.53 ∘Cm−1 × 0.33m = 0.83∘C
Therefore,
The boiling point of a 0.33 m solution in
benzene is (80. 1+ 0.83) = 80.93 ∘C.

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 Depression of Freezing Point
 The decrease in freezing point of a dilute solution
compared to that of the pure solvent, ΔTf, is
called the freezing point depression and is
directly proportional to the molal concentration
of the solute
 ΔTf=Kfm
 where m is the molal concentration of the solute
in the solvent and Kf is called the freezing point
depression constant (or cryoscopic constant).

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 Problem-2
What is the freezing point of the 0.33 m solution
of a nonvolatile nonelectrolyte solute in
benzene? ( as described in problem-1)

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 Osmotic Pressure

Osmotic pressure is the

minimum pressure which
needs to be applied to a
solution to prevent the inward
flow of its pure solvent across
a semipermeable membrane.

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• We can find the osmotic pressure, Π, using the
formula as follows:
• Π = MRT
• where M is the molar concentration, T is the
Kelvin temperature and the value of R is the
universal gas constant.

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 Problem-3
What is the osmotic pressure (atm) of a
0.30 M solution of glucose in water that is used for
intravenous infusion at body temperature, 37 °C?
Solution
We can find the osmotic pressure, Π, using the
formula Π = MRT, where T is on the Kelvin scale
(310 K) and the value of R is expressed in
appropriate units (0.08206 L atm/mol K).
Π= 5.3 atm (Ans)

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 Gas Laws

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 Ideal gas law

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 Homework
Problem #1: Which solution will have a lower freezing point,
one with 25.0 g of NaCl dissolved in 0.500 L solution, or one
with 25.0 g of MgCl2 dissolved in 0.500 L solution?
Problem #2: What is the difference between the molarity and
the molality of a solution? Calculate the molality for a 0.05M
ammonium sulfite [NH4SO3] solution.
Problem #3: Calculate the molecular weight of sulfur if 35.5
grams of sulfur dissolve in 100.0 grams of CS2 to produce a
solution that has a boiling point of 49.48oC. [257 g/mol]
Problem #4: Explain why an 0.100 m solution of HCl dissolved
in benzene has a freezing point depression of 0.512°C, while
an 0.100 m solution of HCl in water has a freezing point
depression of 0.352°C.
Problem #5: What is the freezing point of a solution that
contains 2.50 mol of MgCl2 (ionic) in 600.0 g of water?
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