Neutralization Indicators

Indicators are weak organic acids or bases which change colour according to the H+ ion
concentration of the solution or liquid to which they are added. Like any other weak acid or base,
the indicator is partially dissociated i.e. an equilibrium exists between the un-ionised and ionised
forms. For indicators, the un-ionised form has a different colour from the ionised form. Let us
represent an acidic indicator as HIn. We can thus have an equilibrium equation 3.50 thus

HIn H+ + In-
Colour 1 Colur 2 3.50

Colour 1 and colour 2 being two different colours. In an acidic solution, this equilibria shifts due
to the common ion effect to the left hence colour 1, due to me excess HIn, is observed. However,
in a basic solution, OH- ions react with H+ ions to force the equilibrium to shift to the right hence
colour 1, due to the excess, In- ions, is observed. If the colour of the indicator depends on which
of ihe two HIn or In- is in excess, then if a base is added gradually then we expect that the colour
change will be gradual. This is starting with the colour of HIn and as more H+ ions are removed
and to the colour of In- as more of In- ions are formed

UNIT 4: PHASE EQUILIBRIA

Introduction

A phase is defined as a state of aggregation of molecules of a homogeneous system, i.e. uniform

both in chemical composition and physical state. In unit1 we discussed what makes the three
physical states, gas, liquid and solid different from one another. Depending on the temperature
and pressure the different phases at least of a pure substance can exist in equilibrium. Also, phases
of different chemical composition but same physical state can exist in equilibrium e.g.
liquid/liquid. It is these type of equilibria that we will deal with in this unit. For a pure substance
the various equilibria that can exist at given temperature and pressure can be represented in what
is called a phase diagram e.g. for water, Fig. 4.1 represents its phase diagram.
Fig. 4.1. Phase Diagram for Water

The solid lines represents the conditions under which any two phases exist in equilibrium.

Thus
AT - the sublimation curve represents Solid - Gas equilibria
TC - the melting curve represents Solid - Liquid equilibria
TTC - the boiling curve represents Liquid - Vapour equilibria

At T, the triple point, all the three phases are in equilibrium. Point TC, the critical point represent
the point beyond which the vapour cannot be converted into a liquid by application of pressure
alone, the temperature must be lowered to below TC for the condensation to occur.

The regions where the different phases exist are indicated on the diagram. With the aid of a phase
diagram therefore we can be able to describe precisely the state in which a given substance will
exist at any given temperature and pressure.

4.2: LEARNING GOALS

By the end of this unit you should be able to:
 Describe, with the aid of a phase diagram, the state in which a given substance will
exist at any given temperature and pressure
 Explain the causes of deviation from ideal behaviour for solutions
 Describe the effect of solute concentration on the vapour pressure of a two
component solution.
 Use Raoult’s Law to solve for one variable (Pi, Xi Poi ) given the other two variables
or information from which they can be determined.

4.3: LIQUID – VAPOUR EQUILIBRIA

At any given temperature below the boiling point of a liquid (or liquid mixture) there exists a
vapour, exerting a vapour pressure over the liquid in equilibrium. Indeed the liquid boils when
this vapour pressure, which increases with temperature becomes equal to the external (prevailing)
pressure. This liquid - vapour equilibria is not very important for a pure substance but becomes
interesting in liquid - liquid mixture. Some pairs of liquids (we shall limit our discussion to pairs)
completely mix, and are said to be miscible, while others do not mix, hence immiscible and others
still are partially miscible. Let us consider miscible liquids first. These may form an ideal
solution in which the cohesive forces are just the same as those existing in the separate components
of the solution i.e. forces existing in a solution of A and B are just the same as those existing in
pure A and pure B.

Most variable composition equilibria are represented either at Constant T with P and Composition
as the variables or at Constant P, with T and Composition as the variables.
[A solution is any homogeneous phase that contains more than one component. The component
that constitutes the large proportion is referred to as the solvent and that of lesser proportion the
solute].

Is there an ideal solution?

We look for what we may call an ideal solution with a hope that the concept may lead us to a better
understanding of solutions in general.

Imagine a solution of molecules A and B.

If molecular sizes are the same and intermolecular attraction of A for A and B for B are the same
as the attraction of A for B. The solution is considered ideal when there is a
complete uniformity of intermolecular forces.

4.3.1: RAOULT'S LAW

Partial vapour pressure measures the escaping tendency of a molecule from solution, which in turn
is a measure of the cohesive forces present in solution. This law, discovered experimentally, is
applicable to liquids miscible in all proportions.

Raoult’s Law: It states that at a given temperature the partial vapour pressure of
component I in a liquid mixture is Pi = Pi0 XI where XI is the mole fraction
of that component in the liquid phase, and Pi0 is its saturated vapour
pressure.

Sample Exercise 4.1

At 880C the saturated vapour pressure of benzene and toluene are 953 and 378 mmttg respectively.
Calculate the vapour pressure of a benzene-toluene mixture containing 2 mol of benzene per mole
of toluene, assuming that Raoult's law is obeyed.

Solution:
Here the mole fraction of benzene (XB) and toluene (XT) are 0.66 and 0.33 respectively. Therefore
P = PB + PT = PB0 XB + PT0 XT = (953 x 0.67) + 378 x 0.33) = 763 mmttg.

Practice Exercise 4.1

NOT SHOWN

4.3.2: VAPOUR PRESSURE OF HOMOGENEOUS (TWO COMPONENTS) BINARY

SOLUTION
If each component of the liquid mixture obeys Raoult's law then P1 = P10 X1 and
P2 = P2o (1 - X1). Therefore, at constant T, the total vapour pressure is P = P1 + P2
= P20 + X1 (P1o - P20) P = P10 X1 + P20 (1 - X1)
= P20 + X1 (P10 - P20)

The changes in the total and partial pressures with composition at constant temperature are
represented as below:

4.3.3: DISTILLATION OF BINARY SOLUTIONS

A homogeneous liquid mixture boils when the sum of the partial vapour pressure of its components
equal to the external pressure. In most cases the composition of the vapour differs from that of the
boiling liquid.

If the solution is ideal (i.e. obey Raoult's law) then the composition of the liquid boiling at a
particular temperature is obtained from

Composition of liquid P = P20 + X1 (P10 - P20)

The corresponding vapour composition in terms of mole fraction of component 1 in the vapour
phase, is obtained as follows:

Composition of vapour
0
P1 P X
y1   1 1
P1  P2 P

The above equations relate the liquid and vapour composition at the temperature at which the total
vapour pressure is P. The results of such calculations for liquids of various composition at constant
P can be plotted on a "boiling-point-composition" diagram.
It will be noticed that for systems of this type the vapour is always richer than the liquid in the
more volatile component.

Binary solutions giving boiling-point diagrams similar to the one above can be separated into their
components by successive distillation.

Let us suppose that the original solution has a composition represented by point a. The solution
will boil at a temperature corresponding to b, and give a vapour of composition c, which condenses
to give a liquid of the same composition d etc. Therefore a series of volatisation and condensation
along b-c-d-e-f-g etc, finally produces the pure vapour of the more volatile constituent.

The volatisation - condensation steps described above can be performed in one operation by using
a fractionating column.

In it's simplest form the column consists of a tube loosely packed with a suitable solid material
(e.g. glass beads) and vertically attached to the top of the distillation flask. When the mixture in
the flask is boiled, the vapour condenses at various levels in the fractionating column. The
resultant liquid flows back down the column and is re-volatilised by the upcoming vapour, so that
the a-b-c-d - etc take place automatically. The technique of fractional distillation is of immense
important both in the Laboratory and in various industrial processes (e.g. the refining of
petroleum).

4.3.4: DEVIATIONS FROM RAOULT'S LAW

Deviations arise when the two components (1 and 2) of a binary solution do not exhibit similar
molecular interactions. As a result of these deviations the vapour pressure - composition diagram
is no longer linear, and this in turn affect the shape of the boiling point - composition diagram.
We distinguish two types of deviation.

1) Negative Deviation
This occurs when the attraction between component 1 and 2 is greater than the attraction 1-1 and
2-2. This may be visualized as the holding back of molecules that would otherwise go into the
vapour state. There is a reduction in the vapour pressure of the system. If the deviation is
sufficiently large, the vapour pressure diagram exhibits a minimum, and the boiling point diagram
exhibits a maximum.

Consequently, it is no longer possible to completely separate the components of the system by

fractional distillation. [Consider for example a mixture of initial composition a. Successive
volatisation and condensation will proceed along a-b-c-d - etc so that component 2 will be
preferentially volatilised and the residue in the flask will tend towards composition X, after which
further volatilisations and condensations will produce no further change in composition.

Similarly, if the original mixture is of composition p, the the process will occur along
p-q-r-s- etc and component 1 will be lost while the residue tends towards X. The liquid of
composition X has the highest boiling point and is referred to as an azeotropic or "constant boiling"
mixture. Such mixtures can easily be distinguished from compounds, because their composition
vary with pressure.

Examples: Chloroform/acetone
Cl3CH - - OC(CH3)2 hydrogen bonding
hydrogen chloride/water HCl + H2O  H3O + Cl -

NOT SHOWN

Positive Deviation

This type of deviation occurs when the attractive forces between 1-1 and 2.2 are of similar
magnitudes, but the attraction 1-2 is weaker, so that each constituent vaporises more easily in the
presence of the other. The vapour pressure of the system is greater than expected.
 The result of a large positive deviation

The vapour pressure diagram exhibits a maximum and the boiling-point diagram a minimum.

The distillate composition tends towards Y, a minimum-boiling azeotrope, whereas the residue
becomes richer in either component 1 or 2.

Ethanol/Water at 1 atmosphere 95.6% ethanol boils at 78.20C.

i.e., Fractional distillation cannot completely remove water from aqueous ethanol.

When positive deviations from Raoult's law is sufficiently large, instead of exhibiting azeotropy
the two components may become only partially miscible (eg. phenol and water) or virtually
immiscible (water and chlorobenzene)

4.4: IMMISCIBILITY

Provided a system composed of two immiscible liquids is adequately agitated, so that each liquid
has a chance to vaporise, the total vapour pressure of the system will be the sum of the saturated
vapour pressures of the two components separately.

P = P10 + P20

The system boil at a temperature lower than the boiling points of the two components. This
phenomenon is exploited in the technique of steam distillation whereby a substance immiscible
with water may be distilled at a temperature lower that 1000C by blowing a current of steam
through it. After condensation, the substance and water form two layers which may be separated.
W1 and W2 are masses of the two substances in the distillate, M1 and M2 being their molar masses
and n1 and n2 being the number of moles co-existing in the vapour phase, assuming ideal behaviour.

0
WeightofX MxPx

Weightofwa ter MH 2 0P V H 2 O

At any given pressure P the boiling point of the system may be predicted by plotting P 10 and P20
against T1 and finding the temperature at which P10 + P20 = P.

Sample Exercise 4.2

For n-octane (b.pt = 1260C, M1 = 114x10-3kg mol-1) the steam distillation temperature at 760
mmttg is found to be 900C. At that temperature the saturated vapour pressure of water (P20) is 526
mmttg. How much n-octane will distill over per unit mass of water?

exploited in steam distillation

a substance immiscible with water may be distilled at a temperature lower than 1000C by blowing
a current of steam through it. After condensation, the substance and the water form two layers
which may be separated.
o
W1, W2 massesWof M n1 M1P1 in the distillate
 1substances
1 two

W2 M2n 2 M2P20
M1 and M2 molar masses and n1 and n2 being the number of moles coexisting in the vapour phase
at any given time

boiling point is the T at which P10 + P20 = P

4.5: PARTITION OF SOLUTE BETWEEN TWO IMMISCIBLE SOLVENTS

When a solute (i) is able to dissolve in two immiscible solvents (A and B) in contact, it will
distribute itself between them so that at equilibrium.

(Xi ) A
 KD
(Xi ) B
X - mole fraction

where KD is the distribution coefficient

For dilute solution XI is proportional to concentration C

Ci A  KD
Ci B

This is the basis of liquid-liquid extraction

Eg. a solute (in water is removed by shaking the solution with a immiscible solvent (e.g. ether)
and then separating the two layers.

- Note that, a fixed volume of second solvent will extract more solute if it is used in several
small quantities rather than all at once in a single extraction.

3.9: SOLUBILITY EQUILIBRIA

Solubility is the amount of a solute that dissolves in a specified volume of solvent to give a
saturated solution. According to this definition then, few substances are insoluble since even for
salts like silver chloride, which we refer to as insoluble, in a saturated solution there will be small
amounts of Ag+(aq) and Cl-(aq). It is only because these amounts are so small that we refer to the salt
as insoluble otherwise this is not strictly so. Such salts whose solubilities are very low are said to
be sparingly soluble. In such a saturated solution a heterogeneous equilibrium exists. This is shown
in equation 3.51

AgCl(s) Ag+(aq) + Cl-(aq)

3.51

At equilibrium only 1.67 x 10-3 moles AgCl dissolve in 1 litre of water. We can write the
equilibrium constant for the equilibrium thus as given in equation 3.52

a Ag  .a Cl
K 3.52
a AgCl

Where ‘a’ is the activity. Since the activity of solids is constant then we can write the above
equation as given in 3.53

K sp  K AgCl  [Ag  ][Cl  ] 3.53

Since ‘a’ is equal to the concentration for dilute solutions. This shows that KSP is just a product of
the concentration of the ions in the saturated solution. It is referred to as the Solubility Product.
Other examples include

CaF2(s) Ca2+(aq) + 2F-(aq)

3.54
La(OH)3(aq) La3+(aq) + 3OH-(aq)
3.55

We should note that under no circumstances can the solubility product be exceeded in a saturated
solution and that for concentrations that yield a product of lower value than Ksp, the salt is soluble
i.e. the solution is not saturated. Since solubility is dependent on temperature then Ksp also changes
with temperature.

Sample exercise 3.7

The solubility of AgCl is 1.67 x 10-5 moles per litre at 25 °C. Calculate me solubility product of
AgCl

Upon complete dissociation of AgCl, one mole of the salt would yield separately 1 mole of Ag+
and Cl- ions. Therefore in the saturated solution,

[Ag+] = [Cl-] = 1.67 x 10-5 moles per litre. Therefore the Ksp for AgCl salt is given as

Ksp(AgCl) = [Ag+][Cl-] = (1.67 x 10-5)2

= 2.8 x 10-10mol2l-2

Practice Exercise 3.7

The solubility of Ca(IO3)2 is 2.18 g/l. Calculate the solubility product of Ca(IO3)2
Solubility from Ksp values
If the solubility product is known, then the solubility of the salt can be calculated as illustrated
from the sample exercise 3.8

Sample Exercise 3.8

Given mat Ksp for AgCl is 2.8xlO-10 mol2l-2 at 25 °C. What is die solubility of AgCl in 1 litre
of water?
Solution
-10 2 -2
Ksp(AgCl) = [Ag+][Cl-] = = 2.8 x 10 mol l
 Practice Exercise 3.8
Given tha the Ksp for BaSO4 is 1.08 x 10-10 mol2 l-2, Calculate the solubility in 1 litre
of water

Since KSp cannot be exceeded in a saturated solution any attempt to exceed it by increasing the
concentration of ions results in precipitation so as to maintain K8p. If any of the ions present in the
equilibrium is added from another source, this results in an attempt to increase KSp and therefore
precipitation of the salt occurs. This is in accordance with the Le Charteliers principle. This is
called the Common Ion effect. We can demonstrate this with sample exercise 3.10

Gi ven that Kgp for AgCl as 2.8 x IO-10 M2, determine the solubility of AgCI(s) in 0.1M AgNO3.

Solution
We can only be able to obtain the solubility of AgCl from the concentration of ions since there
as another source of silver ions. From Ksp equation, we know that
AgCl(s) Ag+(aq) + Cl-(aq)
Thus
Ksp = [Ag+][Cl-] = 2.8 x 10-10M2
In absence of the AgNO3, we expect to have
[Ag  ]  [Cl  ]  (K sp )   2.8  10  10   1.7  10  5 M
 

But the contribution of AgNO3 of 0.1M Ag+ in to the solution makes the 1.7 x 10-5
negligible. This suppresses the above equilibrium to the LHS. Thus at equilibrium we will
have
[Ag+] = 0.1M, but [Cl-] will remain unknown. BUT we know that the Ksp value will not
change as long as the temperature is held constant. Therefore
[Ag+][Cl-] = (0.1) x [Cl-] = 2.8 x 10-10
This implies that the [Cl-] = 2.8 x 10-9M. This should as well correspond to the amount of
Ag+ that dissolved from the AgCl salt. Therefore the solubility of AgCl in 0.1M AgNO3 is
2.8 x 10-9M. Truly, this value is much lower than the solubility of the AgCl in pure water.
Refer to sample exercise 3.8

For a salt that is not univaleat, we should be extra careful in deciding the relationship between
concentrations of the ions in the saturated solution to solubility. Consider the practice exercise
3.11

Practice Exercise 3.11

Given that the Ksp for CaF2 is 1.70 x 10-10 M3, what is the solubility of CaF2 in 0.1 M
Ca(NO3)2?
Solution

We obtain the solubility from the concentration of F- in the saturated solution again due to the
fact that there is another source of Ca2+ ions other than CaF2. Solubility will be equal to 1/2 [F-
2+
We can see that the expected Ksp is lower than 1.7 x 10 -10M and hence precipitation will not occur.

In qualitative analysis, say of a suspected Cu2+ and Zn2+ mixture, if we would need to separate the
two ions, We can do so by differential precipitation. Thus, suppose we have a solution containing
0.02 M each of Cu2+ and Zn2+, how can we separate the two? We are provided with the information
that Ksp for ZnS = 1.00 x 10-2 mol21-1 and for CuS = 8 x 10-37 mol2 l-2. The CuS is much more
insoluble compared to ZnS. Given that

Ksp(H2S) = 1 x 10-22M3, that is [H+]2[S] for the reaction

H2S 2H+ + S2-
3.56
Then due to common ion effect we can control the concentration of S by adjusting the [H+]. Thus
-

If we bubble H2S in to a solution of 1M H+ ions, then we will have

[H+]2[S-] = 12[S-] = 1 x 10-22

This implies
[S-] = 1 x 10-22M
If this saturated solution is used in the Zn2+ and Cu2+ mixture, we have then

Ksp(ZnS) = [Zn2+](1 x 10-22) = 1 x 10-2

This implies
[Zn2+] = 1 x 1020M
We do the same for Cu2+ and we obtain that [Cu2+] will be 1 x 10-15M. Clearly, this is an
insignificant amount of Cu2+ ions left in the solution. That way, we will have precipitated copper
from our mix solution. Such a procedure is much utilized in qualitative analysis where ions are
grouped together in inorganic analysis according to their salt solubilities.

SUMMARY
We have seen that acidic solutions are those that contain more H+(aq) than OH-. Basic solutions
contain more OH-. The hydrogen ion is strongly bound to water, for this reason the hydroxium ion,
H3O+is often used to represent the predominant form of H+ in water.

Water spontaneously ionizes to a slight degree (autoionization), forming H+ and OH-. The extent
of ionization is expressed by the ion -product constant for water. At 25 0C, the equation is
represented as

Kw = [H+][OH-] = 1.0 x 10-14

The relationship describes not only pure water, but aqueous solutions as well. Thus, as [H+]
increases, [OH-] decreases.

Strong acids are strong electrolytes, ionizing completely in aqueous solutions. Basic solutions are
produced by ionic hydroxides such as NaOH and by substances that react with water to give [OH-
]. Weak acids are weak electrolytes; only part of the molecules exist in solution in ionized form.
The extent of ionization is expressed by the acid-dissociation constant. A general reaction can be
represented as

HA(aq) H+(aq) + A-(aq)

Weak bases include NH3, amines, and the anions of weak acids. The extent to which a weak base
reacts with water to generate OH- and the conjugate acid of the base is measured by the base-
dissociation constant, Kb. This is the equilibrium constant for the

B(aq) + H2O HB+(aq) + OH-(aq)

where B is the base.

The reaction of ions with water with a resultant change in pH is called hydrolysis. Tlie cations of
strong bases (alkali metal ions and the alkaline earth metal ions) and the .anions of strong acids do
not undergo hydrolysis.

The equilibrium between a solid salt and its ions in solution provides an example of heterogeneous
equilibrium. The solubility product, Ksp, is equilibrium constant that express quantitatively the
extent to which the salt dissolves. Addition to the solution of an ion common to a solubility
equilibrium causes the solubility of the salt to a decrease. This phenomenon is called the common-
ion effect.

Exercise 3

1) The solubility of PbBr2 is 8.4 g I-1 of water. Determine Ksp for PbBr2
2) Ksp for Cu2S is 2.0 x 10-47 m3. Calculate the solubility of Cu2S
3) What is the solubility of BaF2 in 0.20M NaF? K,p BaF2 = 1.7 x 10-6 M3
 4) Does CaCO3 precipitate if 50 ml of 3.0.x 10-5 M Ca(NO3)2 is mixed with 50 ml of 4.0x10-
4
M Na2CO3? Ksp (CaCO3) = 8.7 x 10-9 M2
5) What is the percentage decrease in H+ ion concentration corresponding to an increase of
0.1 in pH?
6) What is the hydrogen ion concentration in a solution with a pH of (a) 4 and (b) 2.3?00
7) 10 ml of a 0.21M NaOH solution is titrated with 0.0911M HCI.
a. What is the pH before addition of any acid
b. What is the pH after addition of 12.00 ml HCI
c. What is the pH at the equivalence point
d. What is the pH after addition of 30 ml HCI
e. Determine the volume at the equivalent point.
8) A buffer solution is prepared by adding 0.02 M HCI to 500 ml of 0.02 M sodium acetate
and then making the volume to one litre with water. Calculate the volume of HCI required
to prepare a buffer solution of pH 5. Ka = 1.75 x 105 for acetic acid.
9) Calculate the pH of a mixture of 50 ml acetic acid with 20 ml of 1M sodium hydroxide. Ka
= 1.75 x 1C"5 for acetic acid.
10) In what equation 9 above what will be the ratio salt to acid ratio if the pH of the solution is
changed to 4.3.
UNIT 5: ELECTROCHEMISTRY

5.1: INTRODUCTION
Electrochemistry is the branch of chemistry that deals with the relationship between electricity
and chemical reactions. The transfer of electrons that occurs during oxidation-reduction reactions
can be used to produce energy in the form of electricity. In other instances, we can use electrical
energy to make certain non-spontaneous chemical processes occur (Electrolysis). We shall begin
our study of electrochemistry by learning the simple galvanic or voltaic cell, labeling the anode,
the cathode and directions of ion and electron movement and the signs of the electrodes and later
discuss briefly electrolysis.

5.2: LEARNING GOALS

By the end of this unit you should be able to:
 Define a galvanic cell
 Represent a cell on a diagram
 Write the anode, cathode and cell reaction for a given cell
 Given appropriate electrode potentials, calculate the emf generated by galvanic cell
 Describe the Hydrogen electrode
 Define Standard electrode potential
 Given appropriate electrode potentials, calculate the emf generated by galvanic cells
 Define electrolysis
 Predict products of simple electrolytic cells

5.3: AN ELECTROCHEMICAL CELL

When a piece of zinc is placed in a solution containing Cu2+ (aq) ions, some of the zinc dissolves
and copper is plated onto the zinc bar. There is a spontaneous “tendency” for this elecron transfer
reaction to take place:

Zn(s)  Zn2+ (aq) + 2e- oxidation

Cu2+(aq) + 2e-  Cu (s) reduction

Zn (s) + Cu2+ (aq)  Zn2+ (aq) + Cu (s) overall reaction

Kc for this reaction is very high. At equilibrium the product Cu and Zn2+ predominate over the
reactants. There is a greater tendency for copper ions to be reduced (gain electrons) than for zinc
ions to be reduced. This tendency has been tabulated as a series of reduction potentials.

If the tendency for the zinc to give up electrons to copper ions were utilized so that electrons
were made to flow through an external circuit, useful electrical work could be done. This is
known as the voltaic or galvanic cell.

Figure 5.1

Electrons flow from the zinc elecrode to the copper electrode. The zinc electrode is negative and
the copper electrode is positive. Oxidation takes place at the anode and reduction at the cathode.

An electrochemical cell or galvanic cell consists of

1. Two conductors (electrodes) immersed in electrolyte solutions

o anode = electrode at which oxidation occurs

Zn(s)  Zn2+ (aq) + 2e-

o cathode = electrode at which reduction occurs

Cu2+(aq) + 2e-  Cu (s)

 2. A salt bridge (to avoid mixing) - in this case KNO3 In order that a charge disparity
produced by the movement of electrons during the operation of the cell can be neutralized
and the electroneutrality maintained eg: in the zinc-copper cell, Zn2+ are produced at the
anode and Cu2+ consumed at the cathode. An overall positive charge in the solution at the
anode and an overall negative charge in the solution at the cathode would prevent further
movement of electrons and the cell would cease to function. The salt bridge allows
migration of ions: anions towards the anode and cations towards the cathode. conduction
of electricity from one electrolyte solution to another - occurs via migration of K+ from
the bridge in one direction and NO3- in the other

3. Voltage measuring device - potential difference is developed by this cell, this potential
difference is a measure of the driving force of the reaction = potentiometer - two
connectors are positive and negative (indicates direction of current) Seen as = if the
concentrations of reactants and products in the cell are far from equilibrium value,
potential difference is very large. If concentration of reactants and products are at
equilibrium, potential difference = 0

Points of Emphasis

1. If concentrations are far from equilibrium, current flowing through circuit can be
harvested - the principle of battery

Battery - electrochemical cell from which we receive energy

Galvanic or voltaic = store electricity - spontaneous chemical reaction to generate

electricity

2. We can also put a battery or power supply across cell and drive the electrochemical
reaction - electrolytic cell = requires an external source of electrical energy - energy
required because we force the reaction to proceed in the opposite direction
3. In a galvanic cell, the anode has a negative charge, and the cathode has a positive charge

Teaching Note: An aid to remembering the signs of the electrodes in a galvanic cell is the
“an” in anode stands for “a negative electrode”

5.4: REFERENCE ELECTRODES AND STANDARD REDUCTION POTENTIALS

A comparison of the “reduction tendency” of various substances can be made. It would be useful
if the potentials for different half-cells could be tabulated. However, the potential of the half-cell
itself cannot be measured: it is possible to measure only the potential difference between two
half-cells. We therefore select arbitrarily a reference electrode relative to which all other half-
cells are measured. The results are tabulated for standard half cells, that is, all reacting species
are at a concentration of 1 M (strictly speaking, at unit “activity”) if in solution or at constant
pressure of 1 atmosphere if a gas.

The Standard hydrogen electrode – SHE

The standard half-cell chosen as the reference half-cell is the standard hydrogen electode; it
contains a platinised platinum electode (inert) dipping into a solution of HCl which is 1 M in
H+(aq) and having H2 gas at 1 atmosphere pressure continually bubbled over the electrode. The
reduction reaction:

H+ (aq) + e-  ½H2(g)

Is assigned arbitrarily a value of 0.00 V, i.e. Eo = 0.00 V at a selected temperature, usually 298
K: Eo is the standard reduction potential, standard indicative relative to the hydrogen half-cell
described above.

The standard reduction potential for Zn2+ (aq) can be measured by setting up an electrochemical
cell which contained H2/H+ aq) (1 M ) in one half-cell and Zn/Zn2+ (aq) (1 M) in the other and
measuring the emf of the cell (all solutions being at the same temperature, usually 298 K). The
emf of the cell is then the standard reduction potential for the reduction reaction

Zn2+ (aq) + 2e  Zn(s) E = -0.76 V

E values for other half-cells can be determined in this way and tabulated. Notice that the
concentrations of the solution in each half-cell is 1 M in the determination of E values. If it is
not 1 M, the value determined is not the Evalue but some other value which depend on the
concentration of the solution.

Detailed tables of E values at 298 K are given in text-books and SI chemical Data.

The more positive the value of E, the greater the tendency for reduction and the better the
oxidizing agent. The more negative the value of E, the lower the tendency for reduction and the
better a reducing agent is the reduction product.

Representation of Cells

Line Diagram: Zn Zn2+(aq) (1 M) Cu2+(aq) Cu

(i) the half-cell of the anode, where oxidation occurs, i.e. the half cell
with the lower reduction potential, is written on the left: the
concentration of the species present is shown in bracket
 (ii) the double vertical lines represent the salt bridge when the half-cell are
not in contact (as in Figure 5.1). The ions or aquated species of the
half-cell should be next to the salt bridge symbol
(iii) the half-cell of the cathode, in which reduction occurs, i.e. the half-cell
with the more positive E (less negative) is written on the right.

Calculation of E Values

The E (emf) of the cell is calculated from

Ecell = Eright - Eleft

Where the E values are both relative to E H2H+ (1 M) being assigned a value of 0.00 V. Notice
that TWO STANDARD REDUCTION POTENTIALS ARE INVOLVED

Eg: for the above cell Ecell = 0.43 – (-0.76) = +1.10 volts

If the cell is correctly written with the anode on the left and cathode on the right and E for the
cell (concentrations 1 M) is calculated as above, then E  0 (positive) and the redox reaction
proceeds in the direction shown, that is, zinc displaces copper ions from solution. A cell so
constructed will produce a voltage of 1.10 V. If E  0 (negative), the spontaneous redox
reaction proceeds in the manner opposite to that written. The spontaneous reaction can be
reversed if a voltage greater than the cell voltage is applied to the cell.

5.5: THE NERNST EQUATION

What factors determine the magnitude of the cell potential?

 Energy is the inherent driving force of reactions. All reactions move to minimize their
energy, so if a lot of energy is released when the reaction occurs, the potential will be
large. This is expressed as the standard electrode potential, Eo.
 Concentration. If concentration is high , Le Chatelier's principle would say the driving
force is greater, therefore the potential is greater

These concentration and electrode potentials are taken into account using the Nernst Equation:

Given a hypothetical reaction:

Ox + ne- ---> Red
Half cell potential associated with this half cell is given by:
E = E0rxn - (RT/nF)ln{[Red]/[Ox]}
0
where E rxn is the thermodynamic driving force for the reaction when the other half-cell of the
reaction is SHE
NOTE: All of these E values are based on writing the equation as a reduction (this is also
known as the standard reduction potential)
Cl2 + 2e- ---> 2Cl- E0 = 1.36 V Strong tendency to occur as a reduction (i.e. as written)
 Na+ + e- ---> Na E0 = -2.71 V Strong tendency to occur as an oxidation (i.e. opposite direction
as written)
If we take the Nernst equation, convert it to base 10, put in the actual values for R and F and
assume we are at room temperature (298K), we get:
E = E0rxn - (0.059/n)log {[Red]/ [Ox]}

Sample Exercise 5.1:

1. Calculate the half-cell potential for Zn electrode in 10-2 M Zn(NO3)2
half-cell reaction: Zn2+ + 2e- ---> Zn
E = E - (0.059/n) log 1/[Zn2+]
E = -0.763 - 0.059/2 log {1/0.01}
E = -0.822 V

Note:
The reaction proceeds as an oxidation, therefore Zn is the anode
This is the cell potential we would get if we assembled the cell:
Any half-cell potential calculated using the Nernst Equation is an E for a hypothetical cell which
has the half cell of interest as the cathode and the SHE as the anode. However, the negative sign
on our example indicates that if assembled, the Zn electrode would be the anode.

Consider the half – cell consisting of the SHE, but P(H2) and [H+] are different! [P{H2} = 0.5
atm and [H+] = 0.01 M]

So, reaction is still:

2H+ + 2e- ---> H2

E = E - 0.0059/2 log {PH2/[H+]} = 0 - 0.059/2 log [0.5/(0.01)2]

E = -0.1093 V

This is how you calculate the half- cell potential, but we would also like to do this for the whole
cell (i.e. when you actually have two half-cells connected to each other).
So, in order to calculate Ecell

 write both half-cells reactions as reductions

 calculate Ecell = ER – EL using Nernst equation
 Ecell = ER – EL

Sample Exercise 5.2

Calculate the Ecell for the following :
Zn /ZnSO4(1.0 M)// CuSO4(1.0 M)/ Cu
anode on left:
Zn2+ + 2e- ---> Zn(s) E = -0.763 V
 Ean = -0.763 -0.059/2 log [1/[Zn2+]]
Eleft = -0.763 V
cathode on right
Cu2+ + 2e- ---> Cu(s) E = 0.337 V
Eright = 0.337 -0.059/2 log (1/1.0)
Eright = 0.337 V
Ecell = Eright - Eleft = 0.337 - (-0.763) = 1.10 V
So, cell reaction is spontaneous as written, the anode reaction is in fact the oxidation and the
cathode reaction is in fact a reduction reaction
So, what if the cell were drawn in this way:
Cu /CuSO4(1.0 M)// ZnSO4(1.0 M)/ Zn
Cu is now anode, Zn is cathode - if you were to follow the same steps, you find that the E for the
cell would be negative. Try this!

Sample Exercise 5.3

Calculate the electrode potential for a Cd electrode in a solution of 0.0100 M Cd2+

Cd2+ + 2 e- = Cd (s) E° = -0.403 V

E = E° - (0.05916/n) log([B]b/[A]a)
E = -0.403 - (0.05916/2) log(1/0.0100)
E = -0.462 V

Sample Exercise 5.4

Calculate the potential for the following cell
Zn | ZnSO4 (5.00 x 10-4 M) || PbSO4 (sat'd) | Pb

Step 1. PbSO4 (s) + 2 e- Pb (s) + SO42- (aq) E° = -0.350 V

Zn2+ (aq) + 2 e- Zn (s) E° = -0.763 V

Step 2. E = E° - (0.05916/n) log([B]b/[A]a)

E+ = E° - (0.05916/2) log (5 x 10-4)
E+ = -0.252 V

Step 3. E- = -0.763 - (0.05916/2) log (1/5 x 10-4)

E- = -0.860 V
Step 4. Ecell = -0.252 V - (-0.860 V) = + 0.608 V
5.6: E° and the Equilibrium Constant
The equilibrium constant for the reaction:
aA+ bB = cC +dD is written as

a cC a dD
Keq  a b where a = activity (concentration)
a Aa B

Therefore the associated Nernst equation can be written thus

RT
E cell  E o  InK eq
nF

When a cell is at equilibrium E=0 hence

RT
Eo  InK eq
nF

Therefore we can calculate Keq from E values.

Sample Exercise 5.6

Calculate the equilibrium constant for the reaction:

PbPb2+ (0.1 M) Ag+ (0.01 M) Ag

E = 0.93 V

0.0257
Then 0.93 = InK eq
2

Therefore In Keq = 72.37

Keq = 2.7 x 1031

Note the high value of Keq since the reaction will go to completion

Sample Exercise 5.7

A piece of copper is placed in a 0.050 M solution of AgNO3. What is the equilibrium constant of
the solution? The reaction is: Cu (s) + 2 Ag+ Cu2+ + 2 Ag (s)
Half-reactions: 2 Ag+ + 2e- 2 Ag (s) E° = 0.799
2+ -
Cu + 2 e Cu (s) E° = 0.399
 E°cell = E+ - E- = 0.799 V - 0.339 V = 0.460 V
K = 10(2(0.460)/0.05916) = 1015.55 = 3.55 x 1015

SUMMARY
Spontaneous oxidation – reduction reactions can be used to generate electricity in galvanic cells.
The electrode at which oxidation occurs is called the anode, and the electrode at which reduction
occurs is called the cathode.

A galvanic cell may be thought to possess a “driving force” that moves the electrons through the
external circuit, from anode to cathode. This driving force is called the electromotive force (emf)
and is measured in volts. The emf of a cell can be regarded as being composed of two parts: that
due to oxidation at the anode and that due to reduction at the cathode (Ecell = Eox + Ered).

Oxidation potentials (Eox) and reduction potentials (Ered) can be assigned to half-reactions by
defining the SHE as a reference:

2H+(1M) + 2e- H2(1 am) E = 0.00 V

Standard reduction potentials are referred to as Standard electrode potentials and are tabulated
for a great variety of reduction half reactions.

The Nernst equation relates emf under non-standard conditions to the standard emf:

2.303RT
E  Eo  log Q
nF

At equilibrium, Q = K and E = 0, so that

2.303RT
Eo  log K
nF

which relates the standard emf to the equilibrium constant K.

EXERCISE FIVE
1. What are the standard electrode potentials and the cell reactions when (a) Zn
electrode and (b) Cu electrodes are connected to the hydrogen electrode

2. Consider the cell made up of Cu/Cu2+ and Ag/Ag+ electrodes

a) Represent the cell on a linear diagram
b) Write the half cell and cell reactios
 c) Determine the emf of the cell
3 For the electrochemical cell represented by
(Pt)Fe3+(aq),Fe2+ (aq) Br- (aq), Br2 (aq) (Pt)
Write the ion-electron half-reactions for reduction at each electrode, and obtain values for
E from SI Chemical Data
Which reduction will be spontaneous? (i.e. which is the cathode reaction?)
What is the anode reaction?
What is the cell reaction?

Colligative Properties
A colligative property is a property of a solution that is dependent on the ratio between the total
number of solute particles (in the solution) to the total number of solvent particles. Colligative
properties are not dependent on the chemical nature of the solution’s components. Thus,
colligative properties can be linked to several quantities that express the concentration of a
solution, such as molarity, normality, and molality. The four colligative properties that can be
exhibited by a solution are:

 Boiling point elevation

 Freezing point depression
 Relative lowering of vapour pressure
 Osmotic pressure
The word “colligative” has been adapted or taken from the Latin word “colligatus” which
translates to “bound together”. In the context of defining a solution, colligative properties help us
understand how the properties of the solution are linked to the concentration of solute in the
solution.

What are Colligative Properties?

Dilute solution containing non-volatile solute exhibit some properties which depend only on the
number of solute particles present and not on the type of solute present. These properties are
called colligative properties. These properties are mostly seen in dilute solutions.
We can further consider colligative properties as those properties that are obtained by the
dissolution of a non-volatile solute in a volatile solvent. Generally, the solvent properties are
changed by the solute where its 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.

Colligative Properties Examples

We can observe the colligative properties of solutions by going through the following examples.
If we add a pinch of salt to a glass full of water its freezing temperature is lowered considerably
than the normal temperature. Alternatively, its boiling temperature is also increased and the
solution will have a lower vapour pressure. There are changes in its osmotic pressure as well.
Similarly, if we add alcohol to water, the solution’s freezing point goes down below the normal
temperature that is observed for either pure water or alcohol.

Different Types of Colligative Properties of Solution

There are different types of colligative properties of a solution. These include, vapour pressure
lowering, boiling point elevation, freezing point depression and osmotic pressure.

1. Lowering of Vapour Pressure

In a pure solvent, the entire surface is occupied by the molecules of the solvent. If a non- volatile
solute is added to the solvent, the surface now has both solute and solvent molecules; thereby
fraction of surface covered by solvent molecules gets reduced. Since the vapour pressure of the
solution is solely due to solvent alone, at the same temperature the vapour pressure of the
solution is found to be lower than that of the pure solvent.

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.
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
2. Elevation in Boiling Point
The boiling point of a liquid is the temperature at which the vapour pressure is equal to
atmospheric pressure. We know that on the addition of a non-volatile liquid to a pure solvent, the
vapour pressure of a solution decrease. Therefore to make vapour pressure equal to atmospheric
pressure we have to increase the temperature of the solution. The difference in the boiling point
of the solution and the boiling point of the pure solvent is termed as elevation in boiling point.
If T0b is the boiling point of the pure solvent and Tb is the boiling point of the solution then
elevation in boiling point is given as
∆Tb =T0b-Tb
Experimental results show that there is a relation between elevation in boiling point and molality
‘m’ of the solute present in solution
∆Tb ∝ m
∆Tb = kb m
Where,
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

3. Depression in Freezing Point

The freezing point of a substance is defined as the temperature at which the vapour pressure of
its liquid is equal to the vapour of the corresponding solid. 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 boiling point of the pure solvent and Tf is the boiling point of the solution then
depression in freezing point is given as
∆Tf =T0f-Tf
Just like elevation in boiling point, depression in freezing point is also directly related to molality
‘m’.
∆Tf = 1000 x kf x m2 / M2 x m1
Where,
k f = molal depression constant
m2 = mass of solvent in g
M1 = mass of solvent in kg
M2 = molar mass of solute

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 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.
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.

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.

Van’t Hoff Factor

When the solute undergoes dissociation or association in solution, the number of particles in
solution increases or decreases and thus, colligative properties changes accordingly. The extent
of dissociation or association of the solute in a solution can be expressed by a factor called Van’t
Hoff.
Solved Problems
1. 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
2. A solution of CaCl2 was prepared by dissolving 0.0169g in 1 Kg of distilled water in (
molar mass of Ca2+= 41g mol– and Cl= 35.5gmol–). The molal depression constant of water is
2kg mol–. The depression in freezing point of the solution is:
Solution:
Van’t Hoff factor(i) of CaCl2 is 3
Kf = 2 kg mol–
Given,
Mass of CaCl2 (m2) = 0.0169g
Molar mass of CaCl2( M2) =112g
Weight of water(m1) =1000g
∆Tf = i x 1000X Kf x m2 / M2 x m1
= 3 x 1000 x 2 x 0.0169 / 112 x 1000g
= 9× 10-4
3. 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
4. On adding non-volatile solute to a solvent which of the following effect is observed;
a. Increase in vapour pressure
b. Increase in freezing point
c. Decrease in osmotic pressure
d. Decrease in vapour pressure
Solution: Option d
In a pure solvent, the entire surface is occupied by the molecules of the solvent. If a non- volatile
solute is added to the solvent, the surface now has both solute and solvent molecules; thereby
fraction of surface covered by solvent molecules gets reduced. Since the vapour pressure of the
solution is solely due to solvent alone, at the same temperature the vapour pressure of the
solution is found to be lower than that of the pure solvent.
5. 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–

Frequently Asked Questions – FAQs

Are Colligative properties physical or chemical?

The physical modifications that occur from applying solute to a solution are colligative
properties. Colligative properties rely on the quantities of solvent particles and the quantity of
solvent, but they do NOT depend on the form of solvent particles, but they do depend on the type
of solvent.

Why are Colligative properties important?

Colligative properties include lowering of vapour pressure, elevation of the boiling point,
depression of the freezing point, and osmotic pressure. As will be defined in this module, this
small set of properties is of fundamental significance to many natural phenomena and technical
applications.

Why is Molality used in Colligative properties?

Molality is not only used in freezing depression points for colligative properties, since the
colligative properties only depend on the number of particles in the solution. Molality, much like
molarity, does not depend on the temperature. Then the volume changes slightly if the
temperature changes, and the molarity will change.

What are the other Colligative properties of solution?

Solutions’ colligative properties are properties that depend on the concentration of molecules or
ions of the solute, but not on the identity of the solute. Colligative properties include lowering of
vapour pressure, boiling point elevation, depression of the freezing point, and osmotic pressure.

What does freezing point depression mean?

Depression from Freezing Point. The freezing point of a solution is smaller than the pure
solvent’s freezing point. This suggests that for freezing to occur, a solution must be cooled to a
lower temperature than the pure solvent.