CLASS XII

Detailed Notes As Per BOARD Examination

CHEMISTRY

CHAPTER-2
SOLUTIONS

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 SOLUTIONS

SOLUTIONS
Introduction:
A solution is a homogenous mixture of two or more substances. The dispersed phase or the substance
which is to be dissolved is called solute, while the dispersion medium in which the solute is dispersed to get
a homogenous mixture is called the solvent.

Types of Solutions:
All the three states of matter (gas , liquid or solid) may behave either as solvent or solute. Depending on the
state of solute or solvent, mainly there may be following nine types of binary solutions.

S.No. Solute Solvent Examples

Solid Solutions
1 Solid Solid All alloys like brass, bronze, an alloy of copper and gold, etc.
2 Liquid Solid Amalgam of mercury with Na, CuSO4.5H2O. FeSO4.7H2O
3 Gas Solid Solution of H2 in Pd, dissolved gases in minerals.
Liquid Solutions
4 Solid Liquid Sugar solution, salt solution, I2 in CCl4
5 Liquid Liquid Benzene in toluene, alcohol in water.
6 Gas Liquid CO2 in water, NH3 in water etc.
Gaseous Solutions
7 Solid Gas Iodine vapours in air, camphor vapours in N2.
8 Liquid Gas Water vapours in air, CHCl3 vapours in N2.
9 Gas Gas Air (O2 + N2)

Units of Concentration:
The concentration of a solution may be defined as the amount of solute present in the given quantity of the
solution. It can be expressed in any of the following ways:

w
Mass percentage   % : It is the amount of solute in grams dissolved per 100 g of solution. e.g., 10%
W
solution of sodium chloride means 10 g of solid sodium chloride present in 100 g of solution.

w weight of solute(g)

 %  100
W weight of solution(g)

v
Volume percentage   % : It is defined as volume of a solute dissolved per 100 ml of solution.
V

v volume of solute

 %  100
V volume of solution

w
Mass by volume percentage   % : It is defined as mass of solute dissolved per 100 ml of solution.
V

It is commonly used in medicine and pharmacy.

w weight of solute(g)

 %  100
V volume of solution(ml)

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SOLUTIONS
Parts per million (ppm): The number of parts of solute present in 1 million parts of solution are called

its ppm. When a solute is present in small quantities (trace amounts), it is easier to express the

concentration in parts per million.

Parts of solute(g/ml/moles)
ppm  106
Parts of solution (g/ml/moles)

Mole Fractions (x):

It is the ratio of number of moles of a particular component to the total number of moles of all the
components.

For binary mixture:

nA
Mole-fraction of component A, xA = ,
n A  nB

where nA is the number of moles of component 'A' and nB is the number of moles of component 'B'.

nB
Mole-fraction of component B, xB =
n A  nB

XA + XB = 1

Molarity (M):

It is expressed as the number of moles of solute per litre of solution.

moles of solute
M
volume of solution in litre

mass of solute (g)  1000

M
molar mass of solute  volume of solution in mL

Unit of molarity: mol L1

Molality (m):

It is defined as number of moles of solute per 1000 g or 1 kg of solvent.

moles of solute
m
weight of solvent in kg

mass of solute (g)  1000

m
molar mass of solute  weight of solvent in g

Unit of molality: mol kg1

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 SOLUTIONS

Normality:

It is defined as number of gram equivalents of solute dissolved per litre of solution.

equivalents of solute
N
volume of solution in litre

equivalents of solute (g)  1000

N
equivalent mass of solute  volume of solution in mL

Unit of molarity: equivalent L1

Some Important Relationship:

1. Molarity × molar mass of solute = Normality × Eq. mass of solute

For Acids, Normality = Basicity × molarity

For Bases, Normality = Acidity × molarity

+
Basicity is the number of H ions given by each molecule of acid in solution.
–
Acidity is the number of OH ions given by each molecule of base in solution.

2. Relationship between molarity and molality -

Molarity (M) and molality (m) are related to each other by the following relation where, d is th density
of solution.

1000  M
m
(1000  d)  M  molar mass of solute 

3. If mass percentage(x) and density(d) is given then molarity can be calculated as

10.d.x
M
molar mass of solute

Solubility:
“Solubility of a substance may be defined as the amount of solute dissolved in 100gms of a solvent to form a
saturated solution at a given temperature”. A saturated solution is a solution which contains at a given
temperature as much solute as it can hold in presence of dissolveding solvent. Any solution may contain less
solute than would be necessary to to saturate it. Such a solution is known as unsaturated solution . When
the solution contains more solute than would be necessary to saturate it then it is termed as supersaturated
solution.

Solid in liquid solution:

It is observed that polar solutes dissolve in polar solvents and non polar solutes in nonpolar solvents. In
general, a solute dissolves in a solvent if the intermolecular interactions are similar in the two or we may say
like dissolves like.

For ionic solutes, the solubility, in general, is related to the magnitude of hydration (or salvation) energy and
lattice energy. In general if the magnitude of hydration energy is greater than lattice energy, the solute is
soluble otherwise it is insoluble.

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Effect of Temperature:
In general, if in a nearly saturated solution, the dissolution process is endothermic ( solH  0 ), the solubility
should increase with rise in temperature and if it is exothermic ( solH  0 ) the solubility should decrease.
These trends are also observed experimentally.

Usually the solubility of the solute increases with increase in temperature (e.g., KI, KNO3, NH4Br ) but in
some cases increase in solubility is negligible (e.g. NaCl ) and in cases of some salts (e.g. CeSO4, NaOH,
Na2SO4) solubility decreases with increase in temperature

Gas in Liquid solutions:

Most of the gases are soluble in water to some extent. The solubility of gas in water generally depends upon
the following factors

(a) Nature of the gas: In general the gases which are easily liquefiable are more soluble in water.

(b) Temperature: The dissolution of gas in water is exothermic process. Hence, the solubility of gas
decreases with rise in temperature.

(c) Pressure: The effect of pressure on solubility of gases in liquid can be given by Henry‟s Law.It
states that “the partial pressure of the gas in vapour phase (p) is proportional to the mole fraction of
the gas (  ) in the solution” and is expressed as: p = KH  Here KH is the Henry‟s law constant.

It is observed from Henry‟s law that Higher the value of KH at a given pressure, the lower is the
solubility of the gas in the liquid.It is also observed that value of K H for a particular gas increase with
increase in temperature

Applications of Henry’s law:

Henry‟s law finds several applications in industry and explains some biological phenomena. Notable among
these are:

(i) To increase the solubility of CO2 in soft drinks and soda water, the bottle is sealed under high
pressure.

(ii) To minimise the painful effects accompanying the decompression of deep sea divers, oxygen diluted
with less soluble helium gas is used as breathing gas.

(iii) At high altitudes the partial pressure of oxygen is less than that at the ground level. This leads to low
concentrations of oxygen in the blood and tissues of people living at high altitudes or climbers. Low
blood oxygen causes climbers to become weak and unable to think clearly, symptoms of a condition
known as anoxia.

Important Points related to vapour pressure:

Vapour Pressure: The partial pressure of vapours in equilibrium with pure solid or pure liquid at a given
temperature. At eq. the rate of evaporation = rate of condensation

e.g. H2O(I) H2O(g)

Kp  pHeq2O,g

Hence V.P is equilibrium constant (KP) of the reaction, liquid vapours.

Vapour pressure of a pure liquid: The pressure exerted by the vapours over the liquid surface at
equilibrium is called vapour pressure. It increases with the increase in temperature.

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 SOLUTIONS
Vapour pressure of solution: The pressure exerted by the vapours of solvent 'A' and solute 'B' in
equilibrium with the liquid phase is called the vapour pressure of solution.

Partial vapour pressure: The pressure of vapours of a component „A‟ over a solution of „A‟ and „B‟ is called
partial vapour pressure of component A. It is denoted by PA.

Raoult’s law: When a non-volatile substance is dissolved in a liquid, the vapour pressure of the liquid
(solvent) is lowered. According to Raoult‟s law, at any given temperature the partial vapour pressure (PA) of
any component of a solution is equal to its mole fraction (XA) multiplied by the vapour pressure of this
component in the pure state ( PA0 ).That is, P
A PA0  XA .

The vapour pressure of the solution (Ptotal) is the sum of the parital pressures of the components, i.e., for the
solution of two volatile liquids with vapour pressures PA and PB.

PT = PA + PB

o

 PA x
APA & PB xBPBo

PT x APAo  xBPBo


(PAo  PBo )x A  PBo

PT 

(PBo  PAo )xB  PAo

PT 

This represents equation of straight line PT v.s. x

Note: If PAº > PBº, A is more volatile than B.B.P. of A < B.P. of B.

Ideal and Non-ideal solution:

Ideal solution: An ideal solution may be defined as the solution which obeys Raoult‟s law over the entire
range of concentration and temperature and during the formation of which no change in enthalpy and no
change in volume takes place. So for ideal solutions the conditions are,
0 0
(i) It should obey Raoult‟s law, i.e., PA = PA XA and PB = PB XB.

(ii) Hmixing = 0

(iii) Vmixing = 0

The solutions in which solvent-solvent and solute-solute interactions are almost of the same type as solvent-
solute interactions, behave nearly as ideal solutions.

This type of solutions are possible if molecules of solute and solvent are almost of same size and have
identical polarity. For example, solutions of following pairs almost behave as ideal solutions,

 n-Heptane and n-hexane

 Chlorobenzene and bromobenzene
 Benzene and toluene

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 Ethyl bromide and ethyl iodide

 Ethylene bromide and ethylene chloride
 Carbon tetrachloride and silicon tetrachloride

Non-Ideal solution: The solutions which do not obey Raoult‟s law and are accompanied by change in
enthalpy and change in volume during their formation are called non-ideal solutions. so, for non-ideal
solutions the conditions are:
0 0
(i) It does not obey Raoult's law. PA  PA XA ;PB  PB XB

(ii) Hmixing 0

(iii) Vmixing 0

Either component of non-ideal binary solution do not follow Raoult's law. The non-ideal solutions are further
divided into two types:

(a) Solutions showing positive deviations. (b) Solutions showing negative deviations.

(a) Solutions showing positive deviation: In this type of deviations, the partial vapour pressure of
each component (say A and B) of solution is greater than the vapour pressure as expected
according to Raoult‟s law. This type of deviations are shown by the solutions in which solvent-solvent
and solute-solute interactions are stronger than solvent-solute interactions.

For the non-ideal solutions exhibiting positive deviation.

PA  PA0 XA ,PB  PB0 XB ; Hmixing 

ve; Vmixing 
ve

e.g. of solutions showing positive deviations

(CH3)2 CO + CS2 ; (CH3)2CO + C2H5OH

C6H6 + (CH3)2CO ; CCl4 + C6H6

CCl4 + CHCl3 ; CCl4 + C6H5CH3

H2O + CH3OH ; H2O + C2H5OH

CH3CHO + CS2 ; CHCl3 + C2H5OH

(b) Solutions showing negative deviation: In this type of deviations the partial vapour pressure of
each component of solution is less than the vapour pressure as expected according to Raoult‟s law.
This type of deviations are shown by the solutions in which solvent-solvent and solute-solute
interactions are weaker than solvent-solute interactions.

For non-ideal solution showing negative deviation.

PA  PA0 XA ,PB  PB0 XB ; Hmixing 

ve; Vmixing 
ve

e.g. of solutions showing negative deviations

CH3COOH + C5H5N (pyridine )

CHCl3 + (CH3)2 CO ; CHCl3 + C6H6

CHCl3 + (C2H5)2O ; H2O + HCl

H2O + HNO3 ; (CH3)2 CO + C6H5NH2

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Differences between ideal and non-ideal solutions

Ideal solutions Solutions with positive Solutions with negative

deviations deviations
A...... B interactions are similar A...... B interactions are smaller A...... B interactions are greater
to A.....A and B.....B than A.....A and B.....B to A.....A and B.....B interactions
interactions interactions
0 0
PA = PA XA and PB = PB XB PA  PA0 XA ,PB  PB0 XB PA  PA0 XA ,PB  PB0 XB
Hsol. 
0 Hsol.  0 Hsol.  0
Vmix  0 Vmix  0 Vmix  0
Do not form azeotrope Exhibit minimum boiling point Exhibit maximum boiling
azeotropy azeotropy

Azeotropic mixture:
Azeotropes are defined as the mixtures of liquids which boil at constant temperature like a pure liquid and
possess same composition of components in liquid as well as in vapour phase. Azeotropes are also called
constant boiling mixtures because whole of the azeotropes changes into vapour state at constant
temperature and their components can not be separated by fractional distillation. Azeotropes are of two
types as described below:

(1) Minimum boiling azeotrope: For the solutions with positive deviation there is an intermediate
composition for which the vapour pressure of the solution is maximum and hence, boiling point is
minimum. At this composition the solution distills at constant temperature without change in
composition. This type of solutions are called minimum boiling azeotrope.

(2) Maximum boiling azeotrope: For the solutions with negative deviations there is an intermediate
composition for which the vapour pressure of the solution is minimum and hence, boiling point is
maximum. At this composition the solution distill`s at constant temperature without the change in
composition. This type of solutions are called maximum boiling azeotrope.

Determining composition of vapour phase:

Let, yA = mole fraction of A in vapour phase of the solution and

yB = mole fraction of B in vapour phase of the solution

Now, we have, PA  yAPT ..... Dalton's law of partial pressure for a gaseous mixture.

PA = xAPA .....Raoult's law

o
Thus, PA = yAPT = xAPA
o
Also PB = yBPT = xBPB

Colligative properties:
All these properties depend on the number of solute particles irrespective of their nature relative to the total
number of particles present in the solution. Such properties are called colligative properties.

Colligative properites  number of particle of solute

Relative Lowering of Vapour Pressure:

The vapour pressure of a solvent in solution is less than that of the pure solvent. Raoult established that the
lowering of vapour pressure depends only on the concentration of the solute particles and it is independent
of their identity.

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SOLUTIONS
Total pressure of a solution (PT) is equal to the sum of partial vapour pressure of solvent P A and partial
vapour pressure of solute PB since solute is non - volatile in nature, so partial vapour pressure of solute PB is
zero(0).

PT = PA + PB ( PB = 0)

PT = PA

PT  PAo x A (xA = 1 – xB)

PT PAo (1  xB )


P
T PAo  PAo xB

PAo  PT 
PAo xB ( PAo  PT 
P lowering in vapour pressure)

PAo  PT PAo  PT
 xB ( = Relative lowering vapour pressure (RLVP))
PAo PAo

PAo  PT nB nB
 ( xB  )
PAo
nA  nB nA  nB

Here nA and nB are the number of moles of solvent and solute respectively present in the solution. For dilute
solutions nB << nA, hence neglecting nB in the denominator we have

poA  p T nB

poA nA

poA  pT w B  MA

poA w A  MB

Here wA and wB are the masses and MA and MB are the molar masses of the solvent and solute repsectively.

Elevation of Boiling Point:

Boiling point: The temperature at which vapour pressure of a liquid becomes equal to the external

pressure present at the surface of the liquid is called b.p of liquid at that pressure.

When a non-volatile solute is added to the volatile solvent then boiling point of solution increase. This
increase in boiling point is known as elevation of boiling point ( Tb ).

B.P of B.P. of
Solvent Solution
1 atm
t
en
Vapour Pressure

o lv
s
re n
Pu ti o Tb
lu
So

Temperature Tbo T b

Let Tbo be the boiling point of pure solvent and Tb be the boiling point of solution. The increase in the boiling
point Tb  Tb  Tbo is known as elevation of boiling point.

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 SOLUTIONS
Experiments have shown that for dilute solutions the elevation of boiling point (ΔT b) is directly proportional to
the molal concentration of the solute in a solution. Thus

Tb  m

or Tb 
K bm (Kb = Molal elevation constant or ebullioscopic constant. )

K  w B  1000 w B  1000
Tb b (m  )
MB  w A MB  w A

Note:
–1
Unit of Kb = K kg mol

Value of Kb depends upon nature of solvent.

–1
For water value of Kb = 0.52 K kg mol .

Depression of Freezing Point:

Freezing point: Temperature at which vapour pressure of solid becomes equal to vapour pressure of

liquid is called freezing point of liquid or melting point of solid.

When a non-volatile solute is added to the volatile solvent then freezing point of solution decrease. This
decrease in freezing point is known as depression of freezing point ( Tf ).
Vapour Pressure

ent
s olv
l iq uid
P u re t ion
t i d S o lu
en Li qu
s o lv
lid
So

Tf Tf
o

Temperature

Let Tfo be the freezing point of pure solvent and Tf be the freezing point of solution. The decrease in the
freezing point Tf  Tfo  Tf is known as depression of freezing point.

Experiments have shown that for dilute solutions the depression of freezing point (ΔTf) is directly proportional
to the molal concentration of the solute in a solution. Thus

Tf  m

or Tf 
Kf m (Kf = Molal depression constant or cryoscopic constant. )

K  w B  1000 w B  1000
Tf f (m  )
MB  w A MB  w A

Note:
–1
 Unit of Kf = K kg mol
 Value of Kf depends upon nature of solvent.
–1
 For water value of Kf = 1.86 K kg mol .

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SOLUTIONS

Osmosis & Osmotic pressure:

Diffusion: The movement of solute particles from high concentration to low concentration is called diffusion.
Osmosis: The movement of solvent particles from high concentration to low concentration through a semi
permeable membrane is called as Osmosis.

 A raw mango placed in concentrated salt solution loses water via osmosis and shrivel into pickle.
 Wilted flowers revive when placed in fresh water.
 A carrot that has become limp because of water loss into the atmosphere can be placed into the
water making it firm once again.
 When placed in water containing less than 0.9% (mass/ volume) salt, blood cells collapse due to loss
of water by osmosis.
 People taking a lot of salt or salty food experience water retention in tissue cells and intercellular
spaces because of osmosis. The resulting puffiness or swelling is called edema.
 Water movement from soil into plant roots and subsequently into upper portion of the plant is partly
due to osmosis.
 The preservation of meat by salting and of fruits by adding sugar protects against bacterial action.
Through the process of osmosis, a bacterium on salted meat or candid fruit loses water, shrivels and
dies.
Osmotic Pressure: The external pressure which must be applied on solution side to stop the process of
osmosis is called osmotic pressure of the solution.

For dilute solutions, it has been found experimentally that osmotic pressure is proportional to the molarity, C
of the solution at a given temperature T.

 CRT

Here  is the osmotic pressure and R is the gas constant.

n 
  B  RT
V

Here V is volume of a solution in litres containing nB moles of solute. If wB grams of solute, of molar mass, MB
is present in the solution, then nB = wB / MB and we can write,

w BRT

MB  V

w BRT
or MB 
 V

 Thus, knowing the quantities wB, T,  and V we can calculate the molar mass of the solute.

 Osmotic pressure is widely used to determine molar masses of proteins, polymers and other
macromolecules. The osmotic pressure method has the advantage over other methods as pressure
measurement is around the room temperature and the molarity of the solution is used instead of
molality. As compared to other colligative properties, its magnitude is large even for very dilute
solutions.

Reverse Osmosis: If the pressure applied on the solution side is more than osmotic pressure of the solution
then the solvent particles will move from solution to solvent side. This process is known as reverse osmosis.
Reverse Osmosis is used for purification of sea water.

Isotonic solution: Two solutions having same osmotic pressure at a given temperature are called isotonic
solutions. For example, the osmotic pressure associated with the fluid inside the blood cell is equivalent to
that of 0.9 % (mass/ volume) sodium chloride solution, called normal saline solution and it is safe to inject
intravenously. On the other hand, if we place the cells in a solution containing more than 0.9 %

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 SOLUTIONS
(mass/volume) sodium chloride, water will flow out of the cells and they would shrink. Such a solution is
called hypertonic. It the salt concentration is less than 0.9% (mass/volume) the solution is said to be
hypotonic. For Isotonic solution 1 2

Abnormal molecular masses:

Molecular masses can be calculated by measuring any of the colligative properties. The relation between
colligative properties and molecular mass of the solute is based on following assumptions.

(1) The solution is dilute, so that Raoult‟s law is obeyed.

(2) The solute neither undergoes dissociation nor association in solution.

In case of solutions where above assumptions are not valid we find discrepencies between observed and
calculated values of colligative properties. These anomalies are primarily due to

(i) Association of solute molecules.

(ii) Dissociation of solute molecules.

(i) Association of solute molecules: Certain solutes in solution are found to associate. This
eventually leads to a decrease in the number of molecular particles in the solutions. Thus, it results
in a decrease in the values of colligative properties. As already discussed, the colligative properties
are inversely related to the molecular mass,

1
colligative property  , therefore, higher values are obtained for molecular
molecular mass of solute
masses than normal values for unassociated molecules.

(ii) Dissociation of solute molecules: A number of electrolytes dissociate in solution to give two or
more particles (ions). Therefore, the number of solute particles, in solutions of such substances, is
more than the expected value. Accordingly, such solutions exhibit higher values of colligative
properties. Since colligative properties are inversely proportional to molecular masses, therefore,
molecular masses of such substances as calculated from colligative properties will be less than their
normal values.

Van't Hoff's Factor:

Van't Hoff introduced a factor is called van't Hoff factor to express the extent of association or dissociation of
solutes in solution.

Since colligative properties are inversly proportional to molecular masses, the van't Hoff's factor may be
written as:

observed colligative property

i
theoretical colligative property

ionization / no. of particles after association

i
ionization/ no. of particles before association

Pobserved Tb observed Tf observed observed

i   
Ptheoritical Tb theoritical Tf theoritical theoritical

In case there is no dissociation or association the value of i become equal to one (unity).

In case of dissociation, the Van't Hoff factor is more than 1.

In case of association, the Van't Hoff factor is less than 1.

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SOLUTIONS
Introduction the Van't Hoff factor modifies the equation for the colligative properties as follows

(i) Relative lowering of vapour pressure

PAo  PT
 ixB
PAo
(ii) Elevation of boiling point
Tb  iKbm
w B  1000
Tb 
i Kb 
MB  w A
(iii) Depression of freezing point
Tf iKf m
w B  1000
Tf 
i Kf 
MB  w A
(iv) Osmotic pressure
 iCRT
i  wB  R  T

MB  V
 In case of dissociation of solute Van't Hoff factor can be given as
1  (n  1)
i
1
Here  is degree of dissociation and n is number of particles after dissociation.
i 1

n 1
 In case of association of solute Van't Hoff factor can be given as

i  1  
n
Here  is degree of association and n is number of particles after association.
n  i  1

1 n

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We serve with some Principles

þ Every student is special.
þ Providing our services through digital learning programs. We aim at developing
self-paced learning with self discipline among the students and to build conceptual
knowledge base of our students.
þ A cost-effective way of learning and enabling students to study at their own pace
and convenience.
þ Largely working to ensure that every student can fully unzip their multidimensional
talent and potential.
þ Always keeping ‘Student First’ and strive hard to continue to meet the needs of our
students.
þ Focussing on high standards of teaching, result-oriented test preparation, healthy
competitive environment.
þ For achieving our mission in consonance with our vision we analyse every task
with fundamentals and accept existing practices along with innovations to move
forward and staying ahead.
þ We never compromise on quality and content.
þ Utilising technology to connect students, parents, teachers, administrators,
bureaucrats & government for the collaborative efforts to transform global society.
þ Facilitating information flow to all those who matter to humanity.

Have any query, you can contact us at

contact@padhloji.com

#PadhnaHaiToPadhloji