Title of the Course: Chemistry of Fertilizer and Radio-Tracer Technique

Course Code: AGCH-107

Topic: Colloid Chemistry

Greek origin = kola (glue) + eiods (like)

The Greek word ‘Kolla’ means ‘glue’ and ‘eiods’ means ‘like’. So colloid means glue like
substance. Thomas Graham was the first man who introduced the colloid in the year 1849 which
is used for a little more than a century. In fact, colloids were prepared and used by man as early
as our civilization itself.

Thomas Graham (1861) studied the ability of dissolved substances to diffuse into water through
a permeable membrane. He observed that crystalline substances such as sodium chloride urea
and sugar passed through the membrane, while others like glue gelatin and gum Arabic did not.
The former he called crystalloids and the latter colloids. So he divided all substances into two
categories
1. Crystalloids: are those substances which diffuse rapidly and pass-
through plant/animal membrane. E.g. sugar, salt, urea etc.
2. Colloids: are those substances which diffuse very slowly and don’t pass
through a permeable membrane. eg, clay in water, glue, gelatin etc.
Colloid is a mixture in which one substance of microscopically dispersed insoluble particles is
suspended throughout another substance. It is a heterogeneous mixture in which particle size is
intermediate of true solution and suspension. Colloids can be made from almost any combination
of gas, liquid, and solid. The particles of which the colloid is made are called the dispersed
material. So Colloid is a heterogeneous system consisting of two phases:

1. Disperse phase and

2. Dispersion medium.
Disperse phase refers to the phase forming particles. It is discontinuous. Dispersion medium is
the medium in which dispersion of the particles takes place and it is continuous. Colloidal
particles float in a medium and do not tend to settle. Some large colloidal particles may settle
very slowly. Colloids are therefore sometimes referred to as dispersed system. In muddy water,
for example, the colloidal particles are tiny grains of sand, silt, and clay. The dispersing medium
is the water in which these particles are suspended.

In milk small fat globules are present as discrete particles in water. Here fat globules are the
dispersed phase and water is the dispersion medium.
Butter Water in fat globules or oil
Fog water in air
Smoke carbon in air
Shaving lather gas globules in liquid soap
Difference between True Solution, Suspension and Colloidal Solution

The table given below summarizes the major properties and points of distinction between each
type of solution with respect to different properties.

Property True Solution Colloidal Solutions Suspension

Size of the < 1nm 1– 100nm >100nm

particles

Nature Homogeneous Heterogeneous Heterogeneous

Filterability Particles of true Colloidal particles Suspension

(Diffusion Solution diffuse cannot pass through particles do not
through rapidly through filter filter paper and pass-through filter
parchment paper as well as through parchment paper and
paper) parchment paper. paper. parchment paper.

Visibility Particles of True Colloidal particles Suspension

Solution are not are not seen to naked particles are big
visible to naked eye. eye but can be enough to be seen
studied through ultra- by naked eye.
microscope.

Tyndall effect True Solution does Colloid shows Suspension may or

not show Tyndall Tyndall effect. may not show
effect. Tyndall effect.

Appearance Transparent Translucent Opaque

Gel: There are some sols that have a high concentration of dispersed solid and change
spontaneously into semisolid form known as a gel. For example,
Gelatin dissolves in warm water to form a colloidal solution which when cooled sets to a
jelly. Gels are formed by interlocking of the dispersed particles in the form of a loose
framework inside which liquid dispersion medium is contained. Many gels shrink if the
fluid component is removed. e.g. by evaporation or freeze drying.

Emulsion: An emulsion is a liquid –liquid suspension that is small drops of one liquid is
dispersed in another liquid. Emulsions are of common occurrence in nature. Milk is an
emulsion. In milk fat globules are dispersed in water.

Size of colloidal Particles:

According to Graham the differences in behavior of “colloids” and “crystalloids” were due to the
particle size. Later it was realized that any substances, regardless of its nature, could be
converted into a colloid by subdividing it into particle of colloid size. In ordinary true solution,
the solute is dispersed throughout the solvent in the form of a single molecules or ions. On the
other hand a suspension contains particles that are large enough to be seen by naked eye or
through the microscope. Colloids occupy an intermediate position between true solution on one
hand and suspension on the other.

Colloidal particles are smaller than the particles of suspension but greater than the articles of true
solution.
Size of the particles in colloid : 1– 100 nm
• Size of the particles in suspension : >100 nm
• Size of the particles in true solution: < 1 nm

1μ = 1/1000mm = 10-3 mm
1 mμ = 10-3/1000 mm = 10-6 mm = 10-7 cm , 1 nm = 10 Å = 10-7cm = 10-9m

Classification of colloids
Colloids are classified according to the following way: -

1. According to the nature of dispersed phase and dispersion medium

A gas may be dispersed in a liquid to form foam (e.g., shaving lather or beaten egg white) or in a
solid to form solid foam.

A liquid may be dispersed in a gas to form an aerosol (e.g., fog or aerosol spray), in another
liquid to form an emulsion (e.g., homogenized milk or mayonnaise), or in a solid to form a gel
(e.g., jellies or cheese).

A solid may be dispersed in a gas to form a solid aerosol (e.g., dust or smoke in air), in a liquid
to form a sol (e.g., ink or muddy water), or in a solid to form a solid sol (e.g., certain alloys).

Dispersed phase and dispersion medium may be present in gaseous, liquid or solid state. Out of
the nine possibilities (3x3) only the combination gas in gas does not lead to a colloidal system
while the remaining eight combinations exist as given below: -

Dispersed Dispersion medium Name of the Example

phase colloidal system

Solid Gas Aerosol Smoke, Iodine vapor

Liquid Hydrosol Clay in water
Solid Solid sol Colored glass, alloys
Liquid Gas Aerosol Clouds,Mist,Rain,Fogs
Liquid Emulsion Milk, Oil in water
Solid Gel Gely, cheese, curd,
Gas Liquid Foam Soap solution, Foam
Solid Solid foam Pumice stone,
2. According to the affinity on solvent.

1. Lyophilic sols (solvent loving)

2. Lyophobic sols (solvent hating)

Lyophilic sols are those in which the dispersed phase exhibits a definite affinity for the medium
or the solvent. Under the influence of electric field the sol particles does move in definite
direction. Depending upon the type of charge, they move towards anode or cathode. Lyophilic
sols are the sols of organic substances.
The examples of lyophilic sols are dispersion of starch, gum, and protein in water. The affinity or
attraction of the sol particles for the medium in a lyophilic sol is due to hydrogen bonding with
water. Dispersion of starch in water, hydrogen bonding occurs between water molecules and the
–OH groups of the starch molecules. Lyophilic sols can be obtained straightway by mixing the
material (starch, protein) with a suitable solvent.
Lyophobic sols are those in which the dispersed phase has no attraction for the medium or the
solvent. Lyophobic sols are not obtained by simply mixing the solid material with the solvent.
Special methods are applied to prepare. Additional stabilizers are required during preparation.
The examples of lyophobic sols are dispersion of gold, iron (iii) hydroxide and sulphur in water.
There are no forces of attraction when sulfur or gold is dispersed in water. These are sometimes
called irreversible sol. Once it is precipitated it is very difficult to convert it into colloidal form.

Difference between Lyophilic sol and Lyophobic sol

Lyophilic sol Lyophobic sol
1. Prepared by direct mixing with 1. Not prepared by direct mixing with the
dispersion medium medium
2. The charge on the lyophilic sol depends 2. The charge on lyophobic sol can be positive
upon pH of the solution and can be or negative. As2S3 sol is negative in nature
negative, positive or neutral. while Fe(OH)3 sol is positive in nature.
3. Lyophilic sols are relatively stable as 3. Lyophobic sols are less stable as weak forces
strong forces of interaction exist of interaction exist between colloidal
between colloidal particles and liquid. particles and liquid.
4. The lyophilic colloids are highly viscous 4. The Lyophobic colloids have almost same
in nature and have higher viscosity than viscosity as that of medium.
that of the medium.
5. Reversible, because on evaporating the 5. Irreversible, because on evaporating the
liquid, the residue left will passes into liquid, the residue left cannot be converted
colloidal state on addition of liquid. into solution on mere addition of liquid.
6. Do not exhibit tyndall effect 6. Exhibit tyndall effect
7. Particles migrate to anode or cathode,or 7. Particles migrate to either anode or cathode
not at all.
8. Precipitated by high concentration of 8. Precipitated by low concentration of
electrolytes. electrolytes.
 3. According to chemical structure, colloids are classified into:

1. Inorganic colloid: Clay minerals, hydrous oxides

2. Organic colloid : Humus, Milk, Cheese, Gels etc,

Inorganic colloids usually make up the bulk of soil colloids. In almost all soils the inorganic
colloids form a major portion of the colloidal complex. It occurs almost exclusively as clay of
various kinds. The chemical analysis of clay indicates the presence of silica, alumina, iron and
combined water. These make up from 90 to 98 per cent of the colloidal clay. Mineral clay
colloids are plate-like in structure and crystalline in nature. The colloidal matter of soil contains
a higher proportion of the important plant nutrients such as Mg+2, Ca+2 and K+.

Organic colloids:
The organic colloids include highly decomposed organic matter generally called humus. Organic
colloids are more reactive chemically and generally have a greater influence on soil properties
per unit weight than the inorganic colloids.

Properties of colloid

Almost all colloids exhibit a number of properties. Some of these properties are given bellow:-

Tyndal effect

An important characteristic of colloid is scattering of light. When a strong beam of light passed
through sol in a dark room, solution becomes luminescent and viewed at right angles to the path
of incident light.

The path of light shows up as a hazy beam or cone. This is due to the fact that sol particles
absorb light energy and then emit it in all directions in space. This effect is termed as Tyndal
effect. The phenomenon of scattering of light by sol particle was studied by John Tyndal, an Irish
scientist and is generally known as Tyndall effect. Real life example of Tyndall effect: When car
headlights or sunlight pass through fog, the light beam becomes visible because tiny water
droplets in the fog scatter the light. Similarly, when a beam of sunlight enters a dark, dusty room
through a window, the dust particles in the air scatter the light, making the path of the beam
visible
 Fig: TYNDALL EFFECT
In a brief, the phenomenon of the scattering of light by the sol particles is called Tyndal effect.
Tyndal effect and other kinetic properties (Brownian motion etc.) have been rendered possible
with the help of ultramicroscope introduced by Zsigmondy in 1903.
Brownian movement:
When a sol is examined with an ultra microscope, the suspended particles are seen as shining
specks of light. By following an individual particle, it is observed that the particle is undergoing
a constant rapid motion.
It moves in a series of short straight-line paths in medium, changing directions abruptly. The
continuous rapid zig-zag movement executed by a colloidal particle in the dispersion medium is
called Brownian movement or motion.
The English Botanist Sir Robert Brown first observed the motion. phenomenon is so named
after Sir Robert Brown who discovered it.

Brownian movement of Colloidal Particles

Explanation of Brownian movement
The explanation of Brownian movement was advanced by Albert Einstein around 1955 by
mathematical considerations based on the kinetic molecular theory. According to him, at any
instant a colloidal particle was being struck by several molecules of the dispersion medium. The
movement of the particle was caused by unequal number of molecules of the medium striking it
from opposite directions.
The movement of the particle was caused by unequal bombardment on the surface of the
colloidal particle by the molecules of the dispersion medium, striking it from opposite directions.
When more molecules struck the particle on one side than on another, the direction of movement
changed. Figure below illustrates how a colloidal particle is knocked about in a zig-zag path by
molecules of the dispersion medium.
 The bombardment on the sides of the colloidal particles by molecules of
dispersion medium causes the random movement of the particle.
In a suspension, the suspended particles being very large, the probability of unequal
bombardments diminishes. The force of the molecules hitting the particle on one side is
cancelled by the force of collisions occurring on the other side. Hence they do not exhibit
Brownian movement.

Fig. Illustration showing how Brownian movement vanishes in coarse suspensions.

The phenomenon of Brownian movement is an excellent proof of the existence of molecules and
their ceaseless motion in liquids. It also explains how the action of gravity, which would
ordinarily cause the settling of colloidal particles, is counteracted. The constant pushing of the
particles by the molecules of the dispersion medium has a stirring effect which does not permit
the particles to settle.
Adsorption: When a solid surface is exposed to a gas or a liquid, molecules from the gas or the
solution phase accumulate or concentrate at the surface. The phenomenon of concentration of
molecules of a gas or a liquid at a solid surface is called adsorption. The substances that
concentrate at the surface are called Adsorbate and the solid on whose surface the concentration
occurs is called Adsorbent. Smaller the particle size, higher the adsorption properties.
Adsorbate

Adsorbent
The surface exposed by colloidal particles is very large for a given weight. Thus the smaller the
size of the particles, the greater the surface area exposed by them. Due to large area surface
exposed by colloidal particles, they have tremendous adsorptive properties.
Electric charge:

Colloidal particles generally carry an electric charge but the system overall is neutral. Since the
dispersion medium carries the opposite charge, in some colloidal system the particles are
negatively charged and in others are positively charged. But ordinarily all particles of a colloidal
system bear a charge of the same sign. The stability of the colloidal suspension is responsible for
the same charge of the particle.

Electrophoresis:
The movement of sol particles or colloidal particles under the influence of an electric field
towards either of the pole, cathode or anode is known as electrophoresis. If electric potential is
applied across two platinum electrodes dipping in a hydrophilic sol, the dispersed particles move
towards one or the other electrode.
The phenomenon of electrophoresis can be demonstrated by placing a layer of As2S3 sol under
two limbs of a U-tube. When a potential difference of about 100 volts is applied across the two
platinum electrodes dipping in deionized water, it is observed that the level of sol drops on the
negative electrode side and rises on the positive electrode side.

Anode Cathode)

Fig A: : Illustration of Electrophoresis

This shows that As2S3 sol has migrated to positive electrode, indicating that the particles are
negatively charged. Similarly, a sol of ferric hydroxide will move to the negative electrode,
showing that its particles carry positive charge. If the sol particles carry a negative charge they
will migrate towards the positive electrode (Anode). This is called anaphoresis.
On the other hand, if the particles are positively charged, they will move towards the negative
electrode (Cathode). It is called cataphoresis. Thus by noting the direction of movement of the
sol particles, we can determine whether they carry a positive or negative charge. Electrophoresis
of positively charged particles (cations) is called cataphoresis, while electrophoresis of
negatively charged particles (anions) is called anaphoresis.

Electrophoresis is a technique used in laboratories in order to separate macromolecules. Using

water as the dispersion medium, the charge on the particles of some common sols determined by
electrophoresis is given below.
NEGATIVELY CHARGED POSITIVELY CHARGED
1. Metals e.g., Au, Ag, Pt 1. Ferric hydroxide
2. Arsenic sulphide 2. Aluminium hydroxide
3. Starch 3. Basic dyes
4. Clay 4. Haemoglobin
Electro-osmosis
A sol is electrically neutral. Therefore the dispersion medium carries an equal but opposite
charge to that of the dispersed particles. Thus the medium will move in opposite direction to the
dispersed phase under the influence of applied electric potential. When the dispersed phase is
kept, stationary, the medium is actually found to move to the electrode of opposite sign that its
own. The movement of the dispersion medium under the influence of applied potential is known
as electro-osmosis.

Fig B: Illustration of Electro-osmosis

The phenomenon of electro-osmosis can be demonstrated by using a U-tube in which a plug of

wet clay (a negative colloid) is fixed (Fig. B). The two limbs of the tube are filled with water to
the same level.
The platinum electrodes are immersed in water and potential applied across them. It will be
observed that water level rises on the cathode side and falls on anode side. This movement of the
medium towards the negative electrode, shows that the charge on the medium is positive.

Similarly, for a positively charged colloid electro-osmosis will take place in the reverse
direction. Technically the phenomenon has been applied in the removal of water from peat (Peat
is partly rotted plant material found in wet, boggy places used as soil improver and sometimes as
fuel), in dewatering of moist clay.

Practical applications of Electro-osmosis:

Electro-osmosis is used in civil engineering to remove water from wet soil or clay foundations.
When an electric field is applied, water moves from the anode to the cathode, helping to dry and
stabilize the soil.
It is used to remove moisture from walls of old buildings, an electric field drives water out of the
damp masonry

Coagulation/Flocculation:
The phenomenon of conversion of colloidal particles to the suspended state (precipitate) is
known as Coagulation or Flocculation. At isoelectric point the particles are completely
uncharged. At this point the colloidal are coagulated or precipitated out of suspension.

Coagulation of a given sol can be brought about by the following ways: -

1. By addition of electrolytes
2. By electrophoresis
3. By mixing two oppositely charged sols.
4. By boiling.

Peptization:

Peptization is the process by which the precipitate or the coagulated colloid reverts to its original
dispersed state or colloidal state is known as peptization. It is the reverse process of coagulation.
When the coagulated colloid is washed, some of the electrolytes responsible for its coagulation is
leached from the internal liquid in contact with the solid particles. In other words it may be
defined as a process of converting a precipitate into colloidal sol by shaking it with dispersion
medium in the presence of small amount of electrolyte. The electrolyte used in this process is
called as peptizing agent.

Soil colloid

The soil colloids are the most active portion of the soil. Inorganic colloids (45%) and organic
colloids (5%) which largely determine the physical and chemical properties of a
soil. Inorganic colloids (Various clay minerals,) usually make up the bulk of soil colloids.
The organic colloids include highly decomposed organic matter generally called humus. Organic
colloids are more reactive chemically and generally have a greater influence on soil properties
per unit weight than the inorganic colloids.

In most soils, there are more clay colloids than organic colloids. Each colloid (clay and organic)
has a net negative (-) charge, developed during the formation process. The negative charge on
the clay mineral surfaces arises largely because of isomorphous replacement of cations in the
crystalline lattices, where trivalent cations are substituted by divalent cations. Cation
replacement in minerals is called isomorphic substitution and occurs predominately in 2:1
minerals, with very little substitution in 1:1 minerals.

Again, the –Al-OH or –Si-OH portion of clay ionizes the H and leaves a temporary negative
charge on the oxygen (-Al-O-, or –Si-O-). The extent of ionized hydrogen depends on solution
pH; more ionization occurs in more alkaline (basic) solutions. In alkaline soil, hydroxyl (OH-)
ions occur predominantly and reacts with the H+, produce water and develops temporary
negative charge on the oxygen (-Al-O-, or –Si-O-).

This negative charge is balanced by thousands of cations. Thus, colloids can be viewed as huge
anions surrounded by a swarm of rather loosely held cations. The negatively charged colloids
attract cations and hold them like a magnet holding small pieces of metal.

Clay particles due to their small size and the plate like structure they expose a large amount of
surface area on which moisture and cations are held. Furthermore, cations themselves hold water.
This hydrated layer of water greatly influences the closeness of charges. As a result the cations
may remain with the negatively charged particles for a long time.

So one of the most important properties of soil colloids is their ability to adsorb, hold, and
release ions. They have an enormous surface area and are negatively charged; hence they can
attract a large number of cations.

In fact colloids have dominant influences on soils physical and chemical properties. Soil colloid
refers to most active portion of the soil and is important to soil properties that greatly affect the
availability of nutrients.
Soil colloids serve very much as a modern bank does. They are the sites within the soil where
ions of essential plant nutrients are held and protected from excessive loss by leaching.
Subsequently, the nutrients can be "withdrawn" from the colloidal "bank" sites and taken up by
plant roots.

In turn, these elements can be "deposited" or returned to the colloids through the addition of
commercial fertilizers, lime, manures, and plant residues.

Role of soil colloid in plant nutrition:

Both the organic and inorganic colloid plays significant role in the nutrient uptake of plants.
Plants obtain nutrients from the following four devices: -
1. through the leaves.
2. from the soil solution.
3. from exchangeable ions on the surface of clay and humus particle.
4. from readily decomposable minerals.

The nutrient cations such as NH4+, K+, Ca2+, Mg2+ and most of the micronutrients are held on
clay particles or clay colloids and humus in an exchangeable and available form for use by
plants.

Due to the property of cation exchange, the soluble inorganic fertilizer nutrients are not washed
away from the soil. For example, when (NH4)2SO4 or K2SO4 are added to the soil NH4+and K+
ions are held on the surface of colloids by cationic exchange and use by plants.

Soil organic matter that serves as the principal storehouse for the anions (NO3-, SO42-, BO33-, and
MoO42-), through the decomposition of organic matter by microorganisms (bacteria, fungi and
actinomycetes etc.) and subsequent oxidation these anions are made available to growing plants
through the soil solution.

Next to photosynthesis and respiration, no process in nature is as important to plants (and

animals) as the soil’s ability to exchange ions (nutrients) between soil colloidal particles and
plants. This important process takes place on the surface of on soil colloid. From the above
discussion, it is clear that soil colloid alone plays a vital role in plant nutrition.

Mechanism of ion adsorption by soil colloids:

Clay and organic matter adsorb nutrients in a plant-available form, that is, the nutrients are
attached to the soil constituents.
The process of nutrient adsorption and release to the soil solution is very important. Organic
matter can adsorb more nutrients than a comparable amount of clay. It is therefore important to
build up the organic matter, especially in soils with less ability to adsorb the mineral component.
The charges associated with soil particles attract ions of opposite charge. Negative charges
generally predominate on the soil particles (colloids), hence adsorbed cations are present in
larger quantities than anions.

Once adsorbed, these minerals are not easily lost when the soil is leached by water and they also
provide a nutrient reserve available to plant roots.

Adsorption of cations

All the cations are not adsorbed with equal tenacity for clay saturated with a given cation. It has
been shown that the replacing power of the alkali metal cation increases with the increase of
atomic weight.

The potassium ion for example is a more powerful replacer than the sodium ion and is more
readily adsorbed by the clay. This same rule holds true for alkaline earth cation.

Further, the higher the valence of the ion, the greater its replacing power and is more readily
adsorbed by the clay. So divalent cations are more readily adsorbed than the monovalent ones.

Hydrogen ion is an exception. It is the most powerful replacer of all cations. Thus the
approximate adsorption of cation series from strongest to weakest is:

H+ = Al+++ > Ca++ = Mg++ > K+ = NH4+ > Na+

Anion adsorption:

Anions are adsorbed by positively charged surfaces in the soil, but only in negligible amounts.
Negatively charged ions, such as nitrate and phosphate anions, are repelled by clay/humus
particles, which are also negatively charged. For this reason, anions are susceptible to leaching
losses in soil solutions. As anions such as nitrate (NO3-), sulfate (SO4-) and chloride (Cl-) are
highly soluble and move with water.

Surface AlOH and FeOH groups are particularly important sites for anion adsorption occurring
on both inorganic and organic complexes. Highest anion exchange capacities are thus found in
acid soils rich in hydrous Fe and Al oxides or in clay minerals or in both. In acidic soils (low
pH), there is an excess of H⁺ ions. These H⁺ ions attach to the surface of soil colloids (especially
oxides of Fe, Al, and clay edges), making the surface positively charged (Fe–OH + H+→Fe–
OH2+). So, soils rich in hydrous oxides with high surface areas are particularly efficient in anion
adsorption. In general the relative order of anion adsorption is:

OH- > PO43- > SO42- > NO3- > Cl-

Cation exchange

The cations that can be replaced on exchange site by other cations are called exchangeable
cations. Ions that are held very tightly with the colloid and they do not pass to the soil solution
very easily. They are called non exchangeable cations.
Cation exchange is the exchange of a cation in the soil solution for another on the surface of a
colloid. Cation exchange is a phenomenon which is constantly going in soils. Both the clay
particles and the organic matter have negatively charged sites that attract and hold positively
charged particles.

As plant roots take up cations, other cations in the soil water replace them on the colloid. Without
some mechanism to temporarily hold cations in the soil, plants would be unable to obtain
sufficient quantities of the essential nutrients to grow. Without cation exchange, the nutrients
would simply be leached downward in the soil and lost.

Cation exchange capacity (CEC).

Cation exchange capacity (CEC) is the total capacity of a soil to hold exchangeable cations or the
ability of a soil to retain cations (positively charged ions) in a form that is available to plants is
known as cation exchange capacity (CEC).

A soil's CEC depends on the amount and kind(s) of colloid(s) present. Although type of clay is
important, in general, the more clay or organic matter present, the higher the CEC. Organic
matter (as humus) always has a high CEC.

The stronger the colloid's negative charge, the greater its capacity to hold and exchange cations,
hence the term cation exchange capacity (CEC). So cation exchange capacity (CEC) is a
quantitative measure of the ability of a soil to exchange cations with the soil solution. Soil pH is
important for CEC because as pH increases (becomes less acid), the number of negative charges on
the colloids increase, thereby increasing CEC.

Units

Cation exchange capacity (CEC) is expressed in terms of centimoles of positive charge per
kilogram cmol(+)/kg) soil.
CEC is also expressed in terms of meq/100 g of soil and these units were often encountered in
textbooks and journal articles. The unit cmol kg-1 is equal to meq/100 g.
Both expressions are numerically identical (10 cmol/kg = 10 meq/100 g )
Movement of Nutrients from Soils to Roots

There are three basic methods in which nutrients make contact with the root surface for plant
uptake. They are root interception, mass flow, and diffusion. Mass flow, diffusion and root
interception, all the three processes are in constant operation during growth. The importance of
each mechanism in supplying nutrients to the root surface for absorption of roots varies with the
chemical properties of each nutrient.

Mass flow:

Mass flow occurs when plant nutrient ions and other dissolved substances are transported to the
surface of roots by the movement of water in the soil. The rate of water flow controls the amount
of nutrients that are transported to the root surface. Therefore, mass flow decreases as the soil
water decreases.

The amount of nutrients reaching the root is thus dependent on the rate of water flow or the water
consumption of the plant and the average nutrient concentration of the soil water.

Mass flow plays an important role for nutrients present in soil solution in high concentration and
when transpiration is high. Under such conditions considerable quantities of water are moved to
the roots carrying various solutes.

The movement of nutrient ions by mass flow will be reduced at low temperatures because the
transpirational demands of plants will be substantially less at low temperatures than under
warmer conditions.
As soil moisture is reduced, water movement slows down. Thus the movement of moisture to the
root surface is slowed. Some mass flow can also take place in response to evaporation and
percolation of soil water.

Movement of ions in the soil solution to the surface of roots is an important factor in supplying
nutrients to plants. Mass flow supplies an over abundance of Ca2+ and Mg2+ in many soils, as
well as most of the mobile nutrients, such as NO3- and SO42-.

Factors influencing mass flow:

Soil moisture, Size of root system, Soil temperature, evaporation, transpiration and nutrient
availability.

Diffusion:
Diffusion is the movement of an ion from a region of higher concentration to a region of lower
concentration. Diffusion comes into operation when the concentration of nutrient ion at the root
surface is either higher or lower than that of the surrounding solution. It is directed towards the
root when the concentration at the root surface is decreased and away from the root when it is
increased.
So diffusion is the movement of a particular nutrient along a concentration gradient. When there
is a difference in concentration of a particular nutrient within the soil solution, the nutrient will
move from an area of higher concentration to an area of lower concentration.

The diffusing particles have a certain pressure called diffusion pressure, which is directly
proportional to the number or concentration of the diffusing particles. Therefore, diffusion takes
place always from a region of higher diffusion pressure to a region of lower diffusion
pressure i.e. along diffusion pressure gradient.

Diffusion is a relatively slow process compared to the mass flow of nutrients with water
movement toward the root.

Root interception:

Root interception is the extension (growth) of plant roots into new soil areas where there are
untapped supplies of nutrients in the soil solution. Thus is a constant operation during growth.
Root interception occurs when a nutrient comes into physical contact with the root surface. As
roots extend through the soil, they continually come in contact with previously unexplored soil.
Therefore root surfaces come in direct contact with nutrients during this displacement process.

So root interception increases as the root surface area and mass increases, thus enabling the plant
to explore a greater amount of soil.

Root interception of nutrients can be enhanced by mycorrhizal fungi, which colonize roots and
increases root exploration into the soil.
Mycorrhiza are a symbiotic association between fungi and the plant roots. This association
increases the root surface area so that roots can extract more nutrients. Mycorrhizae can increase
nutrient uptake by root interception.

Roots usually occupy 1% or less of the soil, however, roots growing through soil pores with
higher than average nutrient content would contact a maximum of 3% of the available soil
nutrients. Generally the amount of nutrients that directly contacts plant roots (interception) is
small as compared with the total nutrient demand. For this reason, mass flow and diffusion
rather than interception are by far the most important process by which plant roots receive their
nutrients.
Factors affecting root interception: Anything that restricts root growth

1. Dry soil
2. Compaction
3. Poor aeration
4. Root disease, insects, nematodes
5. High or low soil temperature

Nutrient transport system

Passive transport:

Passive transport is the transport of ions to roots without the aid of metabolic energy. Ions move
down a chemical potential gradient, i.e. from a higher to a lower concentration.

When the concentration of mineral salts is higher in the outer solution than in the cell sap of root
cells, the mineral salts are absorbed according to the concentration gradient by simple process of
diffusion. This is called passive absorption because it does not require expenditure of metabolic
energy.

Diffusion and ion exchange are passive processes because uptake into outer space is controlled
by ion concentration (diffusion) and electrical (ion exchange) gradients. These processes are
nonselective and do not require energy produced from metabolic reaction within the cell.
It may be simply defined as the absorption of solute by cells according to ordinary laws of
diffusion. Passive absorption takes place through the intimate contact of the root system with the
colloid or soil solution.

Active transport:

The membrane that provides the boundary between the apparent free space and the interior
contents of the cell is the plasmalemma. Since the ion concentrations are greater inside than
outside the cell, transport of ions across the plasmalemma is strictly against an electrochemical
gradient.

Therefore, ion transport across the plasmalemma into the cytoplasm requires energy derived
from metabolism. Absorption and accumulation of mineral salt against the concentration gradient
is an active process, which involves energy. Since ion accumulation is inhibited when the
metabolic activity of the plant is inhibited by low temperatures, metabolic inhibitors and so on.
We can only assume that ion accumulation as it occurs in plants requires metabolic energy.
So active transport is the transport of ions with the aid of metabolic energy.
Theories of nutrient ion uptake mechanism:

Ion uptake mechanism has two steps

The first step in the ion uptake by growing plant is the adsorption of ion by calcium pectate
colloid of the cell wall of the root hair tip and then by cytoplasm.
Second step:
The second step of ion uptake mechanism is the transfer of the adsorbed ion through the
cytoplasm into the cell sap. This transfer is another process which does not take place without
metabolic energy. The adsorption of ions against osmotic gradient can be attained only by the
use of energy which furnishes by respiration.

A number of theories are given by scientist regarding the adsorption of ion. Among the theories
both the contact exchange theory and CO2 theory have been universally accepted by the research
workers.
1. Carbon dioxide theory:

Walker (1960) introduced CO2 theory or solution theory. According to this theory,
1. Respiratory CO2 is released by the root or soil micro-organism.
2. This CO2 forms carbonic acid (H2CO3) on contact with the soil solution.
3. In the soil solution, carbonic acid dissociates into a cation (H+) and an anion (HCO3-).
4. The hydrogen ions (H+) diffuse to clay micelle where they may exchange with cations
adsorbed to the clay surface.
5. The cations thus released into the soil solution from the clay particles and may be absorbed on
root cells in exchange for H+ ions.
6. Or form new ion pair with bicarbonate (example- K+HCO3- shown in the Fig: A) and enters
the root.

Thus, soil solution plays an important role in carbonic acid exchange theory.
Soil microbes
(Micro-organisms)
Soil water
Ca++
Root CO2 + H2O H2CO3 Mg++
Clay micelle
+
H
K+
H+ + HCO3-
+
K NH4+
+ -
K HCO3 Na+

Fig A: Diagrammatic representation of carbon dioxide theory

2. Contact exchange theory:

Hans Jenny and Overstreet (1939) described this theory. The theoretical considerations
developed are based on the concept of overlapping oscillation spaces of adsorbed ions and root
hairs.
Jenny and Overstreet found that there is a direct ionic exchange between the root cells and soil
colloids. According to this theory ions absorbed on clay particle may be exchanged with the ions
on root surface directly without being first dissolved in soil solution (Fig B).

The ions absorbed on the surface of root cells and clay particles (or clay micelles) are not held
tightly but oscillate within small volume of space.

When the root hairs and colloidal particles exist in very intimate contact, the cations of the soil
colloid oscillate around its own axis and also the hydrogen ion of the root cell oscillate around its
own axis.
Whenever the oscillation volume of two ions of similar charge overlaps, one is replaced for the
other. This is termed as contact exchange. As a result ions are absorbed by the plant roots.

Ca++ Ca++
Mg++ K+ Mg++
+
Root H Root

Clay micelle Clay micelle

+ + +
H K H
H+ NH4+ H +
NH4+

Fig. B: Diagrammatic representation of the contact exchange theory.

s
[Ref. Essentials of Physical Chemistry by B.S. BALL and G.D. Tuly
A Text Book of Physical Chemistry by A.S. NEGI and S.C. ANAND]