THEORY

Methods of water treatment can be divided into three categories: physical, biological, and chemical
methods.

Physical methods of water treatment

Physical methods of water treatment usually involve filtration techniques capable of separating
suspended solids, such as sand filtration, multi-media filtration and membrane filtration [1].
Another common physical method is reverse osmosis (RO), whereby contaminants are filtered out
by means of an applied pressure to force water through a semi-permeable membrane. Another well-
known mechanism classified under physical methods of water treatment is adsorption, which was
the mechanism employed during the experiments in this report.

Chemical methods of water treatment

Chemical methods of water treatment are also known as chemical unit processes. One of the many
notable chemical unit processes is coagulation-flocculation, which utilises two methods.
Coagulation method intends to neutralise the charges on the particles in the solution to be treated,
causing small-suspended particles to conglomerate and form microflocs. Here, a rapid and energetic
mix is needed to properly disperse and increase particle collisions. Following this, flocculation is
deployed, whereby gentle mixing is required to bring microflocs into contact with each other.
Collisions from this stage cause microflocs to bond and form visible flocs. Prolonged flocculation
leads to formation of macroflocs until they reach their optimum size. Physical separation methods
such as sedimentation or filtration can now be deployed to separate the macroflocs [2].

Biological methods of water treatment

Biological methods of wastewater treatment are relatively complicated and not fully understood
compared to many physical and chemical water treatment processes, although biological methods
are more effective and economical. These methods utilise bacteria, nematodes, or other
microorganisms for the decomposition of organic wastes via typical cellular processes. The intent of
these biological methods would be to create a system that enables the collection of the
decomposition results for proper disposal [3].

Adsorption

The focus of this experiment is based on the adsorption process for water treatment. This process
refers to the ability of retention of certain desired molecules (adsorbate) on a surface of a material
(adsorbent) in a more or less reversible manner [4]. A commonly-used adsorbent is activated
carbon. One form of activated carbon is granular activated carbon (GAC) that forms a filter bed
through which the water to be treated passes, while the impurities are adsorbed on the surfaces of
the GAC [4]. Another form of activated carbon is powdered activated carbon (PAC), which will be
mixed with the solution to be treated for a short time period, then removed. During this mixing
period is when contaminants will be adsorbed [5].

Although commonly used as a process of water treatment, adsorption would be best suited when the
substance to be removed is sparingly soluble in water. A number of organic substances possess very
few ionizable groups per unit mass of substance, which will form hydrogen bonds with water
molecules. These hydrogen bonds are strong enough to retain organic molecules in the solution.
However, this could be overcomed by a good adsorbent that will reverse the solvation process. This
is due to the greater sum of all chemical bonds after adsorption than before adsorption [6].

Adsorption equilibria

During adsorption, adsorbates will coat the adsorbent surface until equilibrium is achieved between
the adsorbate molecules and the same type of molecules still present in the solution. Whether the
equilibrium could be achieved either with a single layer or multiple layers of the adsorbate on the
adsorbent, depends on the properties of both the adsorbate and adsorbent.

Obtaining the relationship between the adsorbate concentration in solution after equilibrium and the
quantity of adsorbate adsorbed per unit mass of adsorbent requires the plotting of an isotherm. To
construct an isotherm, a standard laboratory procedure could be carried out. Samples of wastewater
containing the adsorbate (may be a specific chemical compound or a group of compounds), are
placed into flasks and added to them are different quantities of adsorbent either in granular form or
powder form. The flasks are then shaken together in a device at constant temperature until all the
contents of the flask have reached equilibrium. This can be seen when the concentration of
adsorbate no longer changes with time. Then, a plot of adsorbate concentration in solution after
equilibrium against the quantity of adsorbate adsorbed per unit mass of adsorbent can be
constructed.

One standardised isotherm model developed by Langmuir is as follows:

𝑞𝑚 𝐾𝑎 𝐶
𝑞= 1+𝐾𝑎 𝐶
(1)

where 𝑞 is the mass of adsorbate adsorbed, 𝑞𝑚 is the mass of adsorbate adsorbed if a complete layer
of one molecule thick is adsorbed, 𝐾𝑎 is a constant and 𝐶 is the equilibrium concentration of
adsorbate in the solution [6].

Several assumptions of the Langmuir isotherm model are [6]:

1. Only a layer of adsorbate molecules will adsorb onto the adsorbent.

2. Adsorbate is immobile once adsorbed.
3. Enthaly of adsorption for all adsorbate molecules are equal.

Factors affecting physical adsorption

An increase in temperature would decrease the degree of physical adsorption. At higher

temperatures, adsorbed molecules will have higher levels of vibrational energies, resulting in the
molecules being more likely to desorb from the surface of the adsorbent. The experiments in this
report were done at a stable ambient temperature in the laboratory so it can be said that the effect of
temperature would be negligible [5].

Typically, adsorption would increase with the increase in surface area of the adsorbent. This applies
to both the external surface area and the internal surface area of the adsorbent. However, large
adsorbate molecules will not be able to adsorb onto much of the internal surface area of the
adsorbent. The solution for this would be to reduce the particle size of the adsorbent [5].
Adsorption would also depend highly on the nature of the adsorbate-adsorbent bond. In a more
technical and quantitative term, it refers to the free energy of interaction between the adsorption
sites and the contact surface area of the adsorbed molecule [4].

The solvent molecules would also compete with the activated carbon surface to attract the adsorbent
molecules, proving that the type of solvent used would affect the degree of adsorption as well. It is
known that organic solvents would compete less with organic adsorbates compared to aqueous
solvents [5].

Researches have shown that it is possible to increase the degree of adsorption of organic adsorbates
onto carbon-based adsorbents using inorganic salts such as sodium chloride and sodium sulphate.
However, care should be taken to not add large amounts of inorganic salts during water treatment
indiscriminately. Appropriate amounts of organic ions adsorbed on the carbon-based adsorbent
surface will cause the repulsion force between adjacent organic ions on the adsorbent surface to be
decreased [5].

Nyex™, the absorbent

It is worth mentioning that despite its desirable properties, AC is expensive and frequently replacing
the saturated AC would be uneconomical. To circumvent this problem, AC would need to be
regenerated so that a continuous process can take place [4]. One way to do this is by supplying an
electrical current to the GAC to oxidise the adsorbates on the surfaces of the AC [7]. Nyex™, the
carbon-based adsorbent in the Arvia Organics Destruction Cell (ODC), has a non-porous nature that
facilitates rapid adsorption of the contaminants [8]. It is also highly-conductive to facilitate the
passage of electric current across its surface for regeneration. Such characteristics reduce the time
needed for both equilibrium and regeneration to be achieved. A significant downside of Nyex™ is
of its reduced adsorbent capacity due to small internal surface area. Nyex™ is a graphite bi-sulphate
intercalation compound, made from flake graphite and a strong oxidising medium with sulphuric
acid present. To provide some context, graphite intercalation compounds are modified compounds
of graphite in which other chemical species have been inserted into the carbon layers of graphite,
resulting in increased distance between the carbon layers, while the characteristic planar structure of
graphite is maintained.

Activated carbon undergo two principal mechanisms to remove contaminants: adsorption and
catalytic reduction. A reason to why the adsorption mechanism is chosen for the activated carbon in
this experiment is for the removal of organic contaminants, for which the catalytic reduction
mechanism would be useless. Organic contaminants adsorb well onto activated carbon due to the
stronger attractive forces between the activated carbon surface (non-polar) and the contaminants
(non-polar), compared to that between the contaminant molecules and water molecules (polar) [9].

Spectrophotometry

Chemical compounds absorb, transmit or reflect light over specific ranges of wavelength. Via
spectrophotometry, the degree of absorbance of light of a certain wavelength can be determined by
measuring the intensity of light when the light beam passes through the sample solution [10].

Spectrophotometry is based on two laws, one of which is called Beer’s Law, which states that the
absorbance of a tested sample is linearly proportional to its concentration [10]:
 𝐴 = 𝜀𝑐𝑋
(2)

where 𝐴 is the absorbance of the sample, 𝜀 is the molar absorptivity, 𝑐 is the uniform concentration
of the sample, and 𝑋 is the path length where the sample solution is confined within.

This equation also states that it is possible to plot a straight line of 𝐴 against 𝑐. This plot is called a
calibration curve, and could be used in estimating the concentration of a sample solution. Beer’s
Law operates under a few assumptions [11]:

1. The radiation is monochromatic and strikes the cuvette at a normal incidence (90ᴼ).
2. Scattering and reflection of the radiation occurs at a minimal, so there are no uncompensated
losses.
3. No molecular interactions between the absorber and other molecules in the sample solution.

Dilution

Dilution, according to Chemistry-Dictionary.com, is the process in which the concentration of a

solute in a solution is reduced, typically done by adding and mixing the existing solution with more
solvent [12]. This concept was crucial in the experiments in this report for the construction of the
calibration curve that would enable the concentration of Acid Violet 17 solutions sampled
throughout the experiments to be easily estimated. The following equation was used:

𝐶1 𝑉1 = 𝐶2 𝑉2
(3)

where 𝐶1 is the concentration of the stock AV17 solution, 𝑉1 is the volume of the stock solution
used to make the diluted solution, 𝐶2 is the final concentration of the diluted solution and 𝑉2 is the
final volume of the diluted solution [13].