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STUDIES ON THE DISPOSAL AND TREATMENT OF SOME
INDUSTRIAL WASTES
DISSERTATION SUBMITTED IN PARTIAL FULFILMENT OF THE REQUIREMENTS
FOR THE AWARD OF THE DEGREE OF
ilgiidIP @ff P)[h)QO@g@p(h)Si' IN
CHEMISTRY
AKHTAR HUSSAIN KHAN
DEPARTMENT OF CHEMISTRY ALIGARH MUSLIM UNIVERSITY
ALIGARH (INDIA)
1 9 8 8
DS1280
Dr. Mohammad Ajmal Environmental Research Lab. Deptt. of Applied Chemistry Z.U. College of Engg.&Tech. Aligarh Muslim University Aligarh - 202 002 iIndia)
Dated . k: JP.. ^.'^. . .
C E R T I F I C A T E
This is to certify that the work described
in this dissertation entitled "Studies on the Disposal
and Treatment of some Industrial Wastes" is the original
work of Mr. Akhtar Hussain Khan, carried out under my
supervision and guidance. The work included in this disser
tation has not been submitted elsewhere for any other
degree or diploma of any university.
MOHAMMAD AJMAL (Supervisor)
A C K N O W L E D G E M E N T
I am highly thankful to Dr. Mohammad Ajmal, Reader,
Department of Applied Chemistry, Aligarh Muslim University.
Aligarh for his guidance, healthy criticism and worthy
suggestions.
My special thanks are also due to Prof. K.T. Naseem
Chairman, Department of Applied Chemistry, A.M.U, Aligarh,
for providing me all the requisite research facilities
available in the department.
I also render my sincerest thanks to
Dr. Ali Mohammad and Dr. Naim Fatima for their kind and
valuable help and suggestions during these studies.
I am indebted to my senior colleagues
Drs. Sultan Ahmad, Ahsanullah Khan, Mujahid A. Khan,
Raziuddin, Nadeem A. Siddiqui and Abdul Jabbar Khan
for their advice, affections and encouragement from time
to time during the all stages of assignment.
I am also sincerely grateful to my colleagues
Rubina Chaudhry and Shamim Ahmad for their moral support
and all round co-operation during the entire period of
studies.
I am no less thankful to my fellow research scho
lars Shahreer Ahmad, Rais Ahmad and Jamal A. Khan for
their assistance and co-operation.
I express heartfelt regards and reverence to my
parents whose good wishes and love have always been
a great source of inspiration in accomplishing this task.
I, indeed feel proud of dedicating this research work
to them.
v - V ^ . v l i > v y ^ ^ - -
(AKHTAR HUSSAIN KHAN)
CONTENTS
Chapter I GENERAL INTRODUCTION
Chapter II SURVEY OF LITERATURES
Chapter III REVERSED PHASE THIN LAYER CHROMATOGRAPHIC SEPARATION OF HEAVY METAL IONS ON SILICA GEL LAYERS LOADED WITH TRIBUTYLAMINE
Introduction
Experimental
Resvilts and Discussion
Chapter IV USE OF ACIDIFIED SILICA GEL LAYERS AS AN ADSORBENT IN CHROMATOGRAPHIC SEPARATION OF SOME METAL IONS
Introduction
Experimental
Results and Discussion
Chapter V SUMMARY
REFERENCES
Page
1-25
26-48
49-55
54-57
58-82
83
84-86
86-97
98-100
101-104
PUBLICATION
1. Reversed Phase Thin Layer Chromatographic
Separation of Heavy Metal Ions on Silica
Gel Layers Loaded with Tributylamine.
Journal of Planar Chromatography
Volume-1, No. 2, pp. 128-15A (1988).
C H A P T E R - I
GENERAL INTRODUCTION
C H A P T E R I
GENERAL INTRODUCTION
It is difficult to define Environmental pollution
and its defination may change not only from country to
country but also from area to area within the same
country. It is, however, less difficult to describe
Environmental Pollution. Such a pollution inclxjdes the
release of substances, which harm the quality of air,
water or soil into the environment which upset the
biological cycles linking man to animals or plants even
when this damage is subtle and causes no deaths or does
not manifest itself for several decades or generations.
Pollution such as noise and smell which often irritates
is also hazardous to health.
We are on stronger ground if we relate pollution
to the natural cycles of growth and decay which, govern
all life on the planet. Where man's activities feed
into and are accomodated within these cycles, he is not
causing pollution. For example, the discharge of carbon
monoxide into the atmosphere by motor vehicles is unli
kely to cause serious overall damage, because natural
bacteria in the soil can feed on it and convert it to
harmless compounds. Provided we do not release so much
carbon monoxide that there are not sufficient bacteria to
break it down, then pollution cannot be said to occur.
On the other hand, the chemicals xxsed as propellants
in domestic and industrial aerosols are not, so far as
we know, attacked by any bacteria and so do not decay
naturally. They cannot slot into any natural cycles
and are therefore steadily building up in the atmos
phere. While there seems no suggestion that they are in
any way dangeroiis at present, they are most certainly
a form of pollution.
Sometimes man's waste products do not merely fail
to form part of the natural cycle, but positively
overwhelm or poison it. Our rivers for example are well
used to receiving natural organic matter and breaking it
down to compounds which can once again become the buil
ding blocks of new plant and animal tissue. When man
adds moderate quantities of domestic sewage, he merely
increases the total load of organic matter to be decayed.
But the bacteria which mainly bring this about need
oxygen to survive and the more the sewage is added the
more oxygen is consumed. Within limits the river natu
rally reaerates itself. But if too much organic matter
is added, the water becomes totally devoid of oxygen.
Not only do fish and other aquatic life die, but so do the
every bacteria which carryout the decaying process. They
are sometimes replaced by other species of bacteria, which
can survive without oxygen, and which can trigger off
different and often dangerous ecological cycles. Either
way, the river has been overwhelmed by pollution.
Some pollutants are indisputably dangerous either
to human health and welfare or to ecological cycles on
which man depends for his survival. I would like to
stress the point that it is quite inadequate to think
of harm to human beings or human health. Man is integral
part of the highly complex web of living organisms which
we call biosphere. Harm done to any part of the biosphere
may have reperexjssions on human welfare, for man relies
on it for food and other raw materials. Many pollutants
have already damaged agriculture and fisheries. We may
conclude that any substance which weakens any link in
nature s network is potentially harmfvil. Pollutants can
be harmful, harmless or even beneficial depending on
their concentration. Carbon dioxide for example, is
essential for green plants, so are the traces of some
heavy materials, so, probably, are small amounts of sulphur
dioxide. Yet large quantities of any of these can skill
plant or animal life.
Again it is easy to determine the effects of a
single pollutants in the laboratory. But in real life
there are usually many pollutants and they may sometimes
have synergistic effects on one another (combined effect
is much greater than the sum of their individual
effects). For example, nitrogen oxides and hydro
carbons emitted from motor car exhausts are relatively
harmless. Together, under the influence of intense
sxjnlight, they can combine to form an eye-smarting
photochemical smog.
One of the important aspects of pollution
abatement pollutes is to strike a balance. On the one
hand we wish to avoid a pollutant reaching a dangerovis
level. On the other than we must not suppress at
great expense which at present is nowhere near a
harmftil level. However, there are certain pollutants
about which there is no controversy. Any pollution
abatement policy shoxjld concentrate upon them.
The Origin of Waste:
One characteristics peculiar to Man is that he
progressively changes his environment to meet his
biological and social needs. On a socially organized
basis Man provides himself with the materials necessary
of life which he removes initially as raw material
from his environment. It is in the provision and
utilization of these material necessities, that worthless
and sometimes harmful by-products originate. Such pro
ducts comprise wastes of ail descriptions and they are
inev i tab le r e s u l t of Man's i n t e rac t ion with h i s physical
and bio logica l sorroundings. To separa te waste from
environment has been one of Man's o ldes t a c t i v i t i e s .
His tor ica l and Cultural Background:
In primit ive nomad s o c i t i e s the problem of waste
d isposal is a t i t s l e a s t . The nomad separa tes waste
from environment by changing his sorroundings. I t i s
when Man ex i s t in permanent communities t h a t the
removal of his waste products must be condixjted on
an organised bas i s . I t i s of i n t e r e s t t o note t h a t
i t was the t r ans i t i on from Pa laeo l i th ic Society based
on hunting and gathering to Neoli thic soc ie ty based on
farming and agricultixre which heralded the need for
waste d isposal . But i t has been the excesses of the
Indus t r i a l Revolution and i t s aftermath upto the
present day which has resul ted in a q u a l i t a t i v e l y
d i f f e ren t type of problem. Although waste disposal
must, as a minimum requirement, conserve the environ
ment's a b i l i t y to sustain human l i f e , the degree to
which i t practised at levels above t h i s rainimtjm depends
on the economic, p o l i t i c a l , cu l t u r a l and aes the t i c
values of the waste producing soc ie ty .
Pollutants.:
Wastes are not necessarily pollutants in them
selves but all have the capacity to be so - A waste
becomes a pollutant when it occurs in a wrong place.
It will be appreciated that production of waste is an
inevitable consequence of the first and second laws
of thermodynamics. The production of actual pollutants
is far from inevitable,
Fredrick Werner (1975) defined a pollutant as
"A substance or effect is normally considered to be a
pollutant if it adversely alters the environment by
changing the growth rate of a species, interferes with
the food chain, is toxic, or interferes with health,
comfort, amenities, or property values of people.
Generally a pollutant is a substqnce or effect intro
duced into the environment in significant amounts as
sewage, waste, accidental discharge, or as a by product
of a manufacturing process or other human activity. A
polluting substance can be a solid, semi-solid, liquid,
gas or sub-molecular particle. A polluting effect is
normally some kind of waste energy such as heat, noise,
or vibration.
Pollution ;
pollution is the result of the action or presence
7
of a pollutant in a part of the environment where it
is considered to have deleterious affects.
In the statement by Darling (1970) : 'Pollution
comes from getting rid of wastes at the least possible
cost.
Odum (1971) says in his own words "Pollution is
an undesirable change in the physical, chemical or
biological characteristics of our air, land and water
that may or will waste or deteriorate our raw material
resources.**
Industrial Wastes:
As a consequences of rapid industrialization in
the post—independence period prior to which our
economy was largely, agrarian, the problem of indus
trial effluent has grown into a significant magnitude.
Since a large majority of indxjstries is water based,
considerable volxme of wastewater emanate from the
indtistries. As the industrial effluents are as
varied in nature as the industry itself, the problem
gets further aggrevated as no standard procedure for
treatment can be recommended. Because of a variety of
reasons the industrial effluents are generally discharged
into water course either untreated or inadeqioately trea-
8
ted. The situation therefore has created a problem of
surface and subsoil water pollution. The pressure on
our water resources is therefore two fold.
(i) Requirement of large volume of water for the
industry and
(ii) Inavailability of clean water because of the
pollution due to the discharge of wastewaters.
In the light of the above it becomes therefore
imperative that the Industrial effluents are
adequately treated so as to become largely inno
cuous. However before the various methods of
treatment and disposal are considered it is
desirable to have a look at the nature of
effluents from various industries.
The growth pattern of some industries in India
which releases hazardous substances which are not bio
logically degradable indicates the increasing serious
ness of the problem is given in the following table.
Characteristics of the Industrial Wastes :
Unlike the domestic sewage, the industrial
wastes are very difficult to generalize. The charac
teristics of the industrial wastes not only vary with
Growth pattern of Some Industries in India :
Production x 10 tonnes
1950
NA
NA
0.25
200
18
I960
1.46*
1.15
1.23
580
153
1970
3.00
13.55
1.79
17,100
1,059
1980
1*0.e&
30.85
5.07
24,100
3,005
Pesticides
Dyes and Pigments
Pharmaceuticals
Organic Chemicals including Petrochemicals
Fertilizers (Nitrogenous and Phosphatic)
Steel ingots
Non-ferrous metals
Copper
Lead
Zinc
Caustic soda
15x10^ 3.4x10^ 6.5x10^ 8.0x10^
NA
NA
NA
11
8.500
NA
NA
101
9.30
1.86
23.41
304
18.80
11.40
52.70
457
+ DDT only ; NA = Not available.
Ref. : Sundaresan, B.B.-, Subrahmanyam, P.V.R.;
I.A.W.P.C. Newsletter, July 1983.
lo
the type of the industry, but also from plant to
plant producing same type of end prodixjts. Different
types of liquid wastes originate from various tjrpes of
industrial processes. The pollutants include the raw
materials, process chemicals, final products, process
intermediates, process by-products, and impurities in
raw materials and process chemicals. Broadly, these
pollutants can be classified as follows :
(i) Organic substances that deplete the oxygen
content of the receiving streams and impose a great
load on the biological units of the sewage treatment
plant.
(ii) Inorganic substances like carbonates, chlorides,
nitrogen etc. that render the water body unfit for
further use and sometimes incourage the growth of some
undesirable micro-plants in the body of water.
(iii) Acids or alkalis which make the receiving stream
unsuitable for the growth of fish and other aquatic life
there, and cause serious difficulties in the operation
of sewage treatment plants.
(iv) Toxic substances like cyanides, sulphides, acety
lene, alcohol, petrol etc. which cause damage to the
flora and fauna of the receiving streams, affect the
11
municipal treatment processes and sometimes endanger
the safety of the workmen.
(v) Colour-prodiicing substances like dyes, which
though not toxic, are aesthetically objectionable when
present in the water sijpplies.
(vi) Oil and other floating substances, which not
only render the streams unsightly but interfere with
the self purification of the same, and the operations
of the sewage treatment plants. A general view of the
natijre of effluents can be had from the following table.
Pollution Characteristics of Different
Industries
Industry Pollution Character- Suggested treat-is tics ment Methods
1. Paper and Strong colour Chemicals recovery pulp
High BOD, Lime Treatment for
High COD/BOD ratio, Colour,
Highly alkaline. Biological Treatment
High sodium content.
12
Industry Pollut ion Character is t ics
Sviggested Treatment Methods
2. Tannery Strong colour, Chemical Treatment ,
High salt content, Biological Treatment
High BOD,
High dissolved s o l i d s ,
Presence of s u l f i d e s ,
Lime and Chromium.
3. Textile Highly alkaline, Chemical and
(a) Cotton High BOD, Biological Treatment
High suspended solids.
High pH .
(b) Synth- Low pH . etic
High dissolved solids.
Toxic organics•
U. Distillary Strong Colour,
and Brewery High chloride ,
High sulphate,
Very high BOD »
and COD, low pH-
Biological
Treatment
5. Petrochemicals
Mineral oils in Chemical Treatment,
various forms. Biological Treatment.
High BOD and COD,
High total solids-
13
Industry Pollution Characteristics
Suggested Treatment Methods
5. Pharmaceuticals
7. Coke oven
8. Oil refin
eries
9. Fertilizer
(a) Nitrogenous
High total solids, Chenical Treatment,
High COD, High Biological Treatment
COD/BOD ratio,
either acidic or
alkaline•
Chemical Treatment,
Biological Treatment
High ammonia.
High pH, High
Phenol content.
High BOD, High
cyanide and
cyanates,Low
suspended solids.
Free and emulsi
fied oil, acids,
alkalis, salts,
phenols, Soaps
and resinoxis or
tarry materials -
High Nitrogen Biological Treatment
content. High pH ,
Oil separation.
Chemical Treatment,
Biological Treatment.
14
Industry Pollution Characteristics
Suggested Treatment Methods
9.(b) Phos-phatic
10. Dairy
11. Sugar
12. Electroplating
High Fluoride
content •
High dissolved
solids, High
suspended solids,
HighBOD, Presence
of oil and grease.
Odors on stagnation*
High BOD, High
Volatile solids.
Low pH .
Biological Treatment
Biological Treatment
Alkaline, Low BOD, Chemical Treatment •
Toxic metals,
cyanides.
Ref. Rao, M.N., Datta, A.K., Waste Water Treatment Oxford IBH Publishing Co. 1979.
From the foregoing table it can be conceived
that the indxjstrial effluents can be categorized into
three broad categories.
( i ) Organic effluents including dairy wastes,
d i s t i l l e ry wastes, tannery wastes etc•
( i i ) Inorganic wastes including electro-plating wastes.
15
Synthetic yarm wastes etc. and
(iii) Toxic wastes covering pesticide wastes, organic
chemical waustes, antibiotic wastes etc. It must however
be mentioned that the categorization is rather arbitrary
and one category does considerably overlape to other.
Volumes of waste waters again vary considerably
from indiastry to industry. A general idea of the
volumes can be had from the following table :
Industry Unit Volumes of waste water per vnit product manufacture
•M57 Gallons/ Unit Unit
1. Pulp and paper
Tonne of paper 50,000 to 227
1000,000 455
2. Straw board Tonne of board 20,000 100
3. Tannery 100 Kg of hide 750 processed
5.^
k. Cotton Textile
1000 meters of Cloth
440-1760 2-8
5. D i s t i l l e r y Tonne of molasses 1320 processed
6. Dairy 1000 l i t r e s of milk processed
440-1760 2-8
16
7.
8.
9.
1
Steel Mill :
Coke oven
Steel (finished)
Refinery-
Fertilizer
Ammonia
Urea
2
Tonne of steel
-do-
Tonne of oil processed
Tonne of NH,
Tonne of Urea
3
125-155
530-650
350-400
2000
1500
h
0.51-0.70
2.^3.0
1.6-1.8
9
7
Ref. : Arora, H.C.
Environmental Pollution Monitoring and Control. Vol. No. 2, HBTI, KanpxjT.
Treatment of Industrial Wastes
Industrial activity is increasingly releasing
gaseous, liquid and solid wastes which are traditionally
discharged to the atmosphere, water bodies including
ocean fronts, or to land, considerably, affecting the
environment.
Some of the main industries are mentioned here
according to the type of pollution and therefore accor
ding to treatability.
- Agriculture and food industries which include
17
sugar refineries, breweries, dairies, cheese dairies.
Slaughter-houses, meat or vegetable preserving plants
cause considerable biodegradable pollution.
The effluents from these industries are laden
with vegetable or animal waste (fibre, fur, hair, fat,
etc.) which block pipes, cause fermentable deposits
and blockages. These also often contain colloidal
or dissolved organic matter which constitutes an
ideal medium fcr fermentation. In some cases, the
waste water contains bacteria or yeast from the manu
facturing process. Effluents from fish canneries and
curing plant may be heavily polluted with salt.
The composition of the effluents often varies
considerably over a period and it may be advantageous
to install buffer tanks for storage and homogenisation.
The biological treatment processes used for
these effluents are generally the same as for domestic
sewage, but high purification efficiency is required
because of the large amount of pollution to be treated.
Furthermore the presence of glueids and rapidly fermen
table products encourages the development of some
types of microorganisms which may interfere with the
efficient operation of the treatment plant.
18
Low rate treatment processes are therefore used.
Secondry clarifiers are generously scaled and pretreat-
ment processes such as grit and grease removal by
static means or by air injection fine screening or
microstraining must be particularly efficient. Aerated
lagoons, providing extensive storage facilities though
wasteful of energy, are particiiLarly recommended for
these indxostries on conditions that preliminary treat
ment processes are carefully planned and the lagoons and
aerators designed for maximun reliability.
The manxifacturing circuits should be studied
in detail before a treatment plant is constructed, as
it is advantageous to separate certain heavily -
polluting effluents sxochas mother liquor and serums at
the source, since the very considerable and specific
pollution involved may require separate recovery or
destruction (e.g. methanation).
Stabilization and dewatering of the biological
sludge is an essential adjunct to purification. The
most modern processes should be used so as to reduce
the relatively high operating costs in this type of
indvistry.
The paper-making industry is the third largest
19
source of i ndus t r i a l organic po l lu t ion a f t e r stock
breeding and the food indxjstr ies, the po l lu t ion i t
produces representing 10 percent of a l l indxjstrial
po l lu t ion in advanced coun t r i e s .
About one t h i r d of t h i s po l lu t ion cons is t s of
the white water from the actxial manufacture of paper,
while the other two-thirds a r i s e from the manufacture
of the various mechanical, semichemical, b i s u l p h i t e ,
k r a f t , unbleached or bleached piilps.
Though simple physico-chemical treatment of the
the white water by f loccula t ion and s e t t l i n g or f loa
t a t i on can eleminate the considerable suspended sol ids
and 50 to 70 percent of the BOD, treatment of the pulp
manufacturing eff luents presents d i f f i c i i l t i e s l inked
to t h e i r colour due to l i gn in and t o the presence of
other compounds which are not eas i ly biodegradable.
I t requires complicated pretreatment (removal of colour
by the Degremont aluminium sulphate process from the
bleached kraf t piilp ef f luent , removal of sulphides
from the unbleached kraf t puLp eff luent e t c . ) . In a l l
cases, high r a t e b io logica l treatment should remove
the BOD which can vary from 10 Kg/t in the case of
mechanical pulp to 250 Kg/t in the case of Kraft pulps
without l iquor recovery.
20
The polluted effluents from the various manu
facturing processes in the automobile and metal fini
shing industries may be classified under three cate
gories according to source electroplating and heat
treatment shops, chemical deposition or etching,
picking plant, paint shops, and machining, grinding
or screw-cutting shops (soluble oils).
The first type consists of acid or basic inor
ganic pollutants or toxic pollutants (cyanides, hexa-
valent chromium, fluorides and heavy metals and
small quantities of organic surface active) pollutants.
Whether these effluents are discharged direct
or recycled via an ion exchange unit, it is necessary
to detoxify the final effluent by neutralisation, pre
cipitation of metal hydroxides, oxidation of toxic
hexavalent chromium. The organic matter can be fixed
on adsorbents.
Metal concentrations in acid baths can be
stabilised by ion exchange.
The second type of effluent corresponds in the
application of three successive coats of point-primer,
londercoat and the glass. The development of the
primer from electrophoresis (anaphoresis and cata-
phoresis) produces specific effluents which are treated
21
by floccialation and floatation in special Defire-
ment floatation units. The more highly polluted
effluents from the point slops are salted out in
situ by flocculants after which they are briefly
clarified and recycled. The recycled effluent must,
however, be deconcentrated and the blowdown treated
by flocculation and floatation.
Soluble oils are difficult to treat as the
paths used in this industry are highly concentrated
and have to be treated in plants varying greatly in size
and equipment. This type of effluent is treated by the
following processes : flocculation-floatation, ultra
filtration, reverse osmosis, possibly hot breaking or
incineration in exceptional cases. The process is
chosen according to the formula of the lubricants used.
The effluents from the petroleum refining and
petrochemical industries, which are separated according
to origin from the units or drains are treated in two
or three stages according to the nature and concentra
tion of the pollutants. These are mainly aliphatic or
aromatic hydrocarbons plus a wide variety of organic
and mineral compounds (phenols, mercaptans, sxilphides,
fluorides, organic acids, etc.).
The first stage consists of preliminary oil
22
removal by gravi ty separa t ion in two successive phases
intended to recover the free o i l s (Degremout c i r c u l a r
o i l removal u n i t ) .
The second or physical-chemical s tage ensures
coagulation of the emulsified o i l s by means of e i t he r
an organic coagulant or a metal hydroxide and poss ible
p rec ip i t a t i on or oxidation of the sulphides . The f loe
formed can be separated with excel lent r e su l t s in Flotazur
or sed i f lo tazur f l oa t a t ion tanks . In some cases o i l may
be removed by f i l t r a t i o n throi:igh sand or dual media
f U t e r .
The th i rd s tage i s necessary only when elemina-
t ing res idual BOD or phenol compounds. I t cons is t s of
b iological piorification carr ied out by Degremont in
three ways according to the nature and concentrat ion
of the soluble BODc- by high r a t e act ivated sludge
treatment, or by extended aera t ion;
By coordinated-material b io log ica l f i l t e r s ;
by pressiorised b io logica l f i l t e r s , or p i o l i t e
f i l t e r s -
Among other i ndus t r i e s , the iron and s t e e l
industry h i the r to produced p l lu t an t s in the form of
eas i ly separate suspended s o l i d s . However, advanced
technology i s tending to cause addi t iona l po l lu t ion by
dissolved s a l t s or o i l .
23
In the chemical and pharmaceutical industries,
where the manufacturing process is often intermittent,
rapidly changing technology necessitates constant
rethinking on treatability and often requires specific
pretreatment in the treatment units or special preli
minary techniques (e.g. stripping, carbonate removal,
oil removal etc.).
The textile manufacturing indvistries present
spacial problems in the reduction of colour and soluble
CX)D.
In fossil fuel and nuclear power station, where
waste streams produce pollution which often passes
unnoticed but which requires special treatment, such
effluents can often be recycled.
Disposal of Industrial Wastes
The treated effluents can be discharged into
surface water courses, sewers and onto land. The mode
of disposal however has to depend on the merits of
the case so that the problem of pollution can be mini
mized if not totally eleminated. It is important to
bear in mind that some of the stabilized industrial
effluents have a good manurial potential which should be
exploited. This practice will not only be useful for
our soil but also would be a good step towards minimizing
24
pollution. Neverthless it has to be ensured that the
treated effluent is safe enough to be lised for irriga
tion purposes.
Wastes are disposed off on land in two forms,
the solid wastes and the liquid wastes. The liquid
wastes include, sewage, sewage effluents and industrial
effluents. The disposal of these liquid wastes on land
is done by two distinct methods.
(i) Irrigation - wherein sewage or industrial waste
waters are utilized in raising profitable crops while
simultaneously affording satisfactory hygenic disposal.
(ii) Infiltration - of sewage or industrial waste
waters on land prepared for mere infiltration and dis
posal without any profitable crop raising, such vegeta
tion as may be permitted on the infiltration area should
be only for the purpose of facilitating or increasing
the rate of disposal by improving the conditions for
the dissipation of sewage or industrial effluents by
the action of roots and axjgmenting the rate of overall
disposal per unit of area by evapotranspiration losses
induced vegetation.
The harmful effect or infertility of sewage or
industrial waste - irrigated soils is due to any one
or combination of the following factors.
25
(i) Difficulty of carrying out agriciiltiiral
operation.
(ii) Anaerobic conditions in soil,
(iii) Restriction of root zone of plants.
(iv) Smothering of the crops by the flora of water -
logged lands.
(v) Possibility of a high concentration of salts
particularly sodium salts.
Salt may retard absorption of nutrients and water,
may themselves be toxic, or lead to alkailine conditions.
Anaerobic conditions also retard the bacterial activity
which is essential for nitrification.
Scientists are continuously assessing the possi
bilities of disposing of sewage sludge, municipal waste
water and the trade wastes on the land and on the utili
zation of the nutrients present in these wastes by the
crops.
C H A P T E R - II
SURVEY OF LITERATURES
26
C H A P T E R 2
SURVEY OF LITERATURE
Sco t t (1980) r epo r t ed a su lph ide p r e c i p i t a t i o n
process t h a t can be ijsed t o remove heavy meta ls from
waste s t reams and y i e l d s a su lph ide s ludge s u i t a b l e fo r
l a n d f i l l . The waste t r ea tment system c o n s i s t s of nex>-
t r a l i z a t i o n , p r e c i p i t a t i o n , c l a r i f i c a t i o n , f i l t r a t i o n
and s ludge dewate r ing .
Lead, Germanium and Zirconium in was tewate r
from semiconductor manufacture o r a n u c l e a r r e a c t o r
a re removed by p r e c i p i t a t i o n (Kosaku, 1980) . The
wastewater i s a e r a t e d a t pH 7-9 in t h e p re sence of a
c a r b o n a t e , then a f e r rous s a l t and an a l k a l i n e
compound a r e added ( t o pH 9-11) t o p r e c i p i t a t e t h e
m e t a l s . Thus a wastewater (pH 8.02) con ta in ing
75 .5 ppm germanium and 3360 ppm F luor ide was a e r a t e d
in t h e p resence of Na2C0,, and an FeSO^ s o l u t i o n was
added. Calcium Hydroxide was then added t o pH 1 0 , and
an an ion ic polymer coagulant was added, fol lowed by
n e u t r a l i z a t i o n . The superna tan t l i q u i d con ta ined no
germanium.
Kotani e t a l s (1980) t r e a t e d t h e l ead c o n t a i n i n g
wastewater by s o l i d i f i c a t i o n with c o n c r e t e or cement in
21
the presence of a harmless metal sialfate. Thus lead
containing pigment slvxige was mixed with aluminium
sulphate and cement. No lead was leached out a f t e r
five weeks.
Lyubman e t a l s . (1981) car r ied out the p r ec ip i -5 + t a t i on of As from water solut ions containing sulphuric
acid and arsenic and determined the optimum conditions
for the most e f fec t ive p r e c i p i t a t i o n of As- from sxol-
phuric acid and As-containing waste waters. The most 5+ effect ive p r e c i p i t a t i o n of As was achieved when calcium
hydroxide was lised as a p r e c i p i t a t i n g agent a t 80° and
a t pH 12.0-12.5 .
Electro-plating wastewater containing cyanide is
treated with sodium hypochlorite, (Thomas et als, 1981)
for conversion of cyanide to cyanate, and to carbondi-
oxide and nitrogen. The cyanide concentrations before
and after the treatment are 30 and 0.50 mg/L, respec
tively. The cyanide free wastewater containing metals
is treated with sodium hydroxide in two stages for proper
metal hydroxide precipitation followed by flocculation
for copper and nickel, the removal rates are /N-< 95 percent,
for silver and tin, '•>^ 75 percent.
Teslya et als. (1981) suggested the removal of
heavy metals from wastewater giving reduced amounts of
28
toxic wastes and reiJsable water by treating at pH 4-5
with the reaction product of a fayalite slag and a>SO^
and increasing the pH to 7-8.5 to precipitate the heavy
metals.
Higgins et als. (1982) suggested the treatment
of heavy metals wastewater by alkaline ferrous reduction
of chromium and sulfide precipitation. Ferrous sulphate
reduces rapidly and stoichiometrically the Cr(VI) in
synthetic plating rinse waters at a pH 7-10. Sodium
sulphide and ferrous sulphate act synergistically. The
oxidized Fe(II) ion coagxilates colloidal metal sxalfides.
Alkyl and EDTA, but not Ca hardness interfere with Cr
reduction, floe formation, and removal. Treatment
using FeSO^ and Na^S precipitation/coagulation followed
by direct upflow filtration provides effective removal
of chromium and cadmium from the rinse water.
The mechanism of adsorption of Iron on activa
ted carbon has been studied by Nakamori et als. (1982).
The adsorption isotherms conform to the Freundlich
equation. The amount of iron adsorbed is a function
of the H concentration. Iron is not adsorbed as
Fe- . Fe is not adsorbed from a O.Cl N H d soln. on
activated carbon. Fe(0H)2 is the adsorbed species.
Balykin (1982) reported the removal of mercury
29
from wastewater by filtering through activated carbon
is improved by pretreating the activated carbon with
a 20-25 percent solution of sodium thiosiilphate and
pH adjustment of the wastewater, frcxn 1 to 7.
Gregory et als. (1982) sioggested that, adsorbing
colloid foam floatation can be effectively x;>sed in
industrial wastewater treatment to remove copper, zinc,
chromium and mixtures thereof. Thus under optimal
conditions in pilot plant treatment, the copper (II)
and zinc (II) concentration in the treated effluent
was 0.1-0.3 and 0,5 mg/L respectively. Treatment of
electroplating wastewater containing copper (II), zinc
(II) and chromium (III) in concentrations of 20 mg each/L
produced effluent containing < 0.1 mg copper (II),
< 0.5 mg Zinc (II), and 1 0.2 mg chromium (III)/L.
The method was found to be more economically and advan
tageous than other conventional methods.
Mercury was effectively removed from industrial
wastewaters by precipitation with NaHS and subsequent
oxidation of excess NaHS with ferric chloride to prevent
the formation of ferrous si£Lphide and zinc sulphide
which could produce HpS after landfilling of the sludge
(Gechmann and Hennings, 1982).
Chisso Corp. (1982) reported that a wastewater
30
containing chromium (VI) and f luor ide i s reduced,
neutra l ized with calcium hydroxide, then, the resu l t ing
sl\jrry i s so l i d i f i ed with gypsum. The method can t r e a t
a Cr "*" and f luoride containing wastewater simxaltaneously.
Thus a wastewater containing Cr and sulphxjric acid was fit 2 t
t rea ted with MeOH to reduce Cr to Cr- , then t rea ted
with calcium hydroxide. Another wastewater containing
Cr and F was reduced with MeOH, then t rea ted with
calcium hydroxide. The two re su l t ing s l u r r i e s were
molded and cured for d isposal .
Petryaev et a l s . (1982) s t i r l ied the removal of
arsenic by passing Na^OOa-containing wastewater through
a cation exchanger r esu l t ing in the formation of HpCO r
and through an anion exchanger to remove carbonate.
The degree of pur i f i ca t ion is increased by aerat ing
wastewater a f te r passing through the cat ion exchangev
with a res idual concentration of 20-30 mg H^OO^/L.
Konkova (19B3) reported the use of indiostrial
wastes for the removal of heaA/y metal ions and petroleum
products from indus t r i a l wastewater. The removal of iron
and copper from wastewater using sawdust and an th rac i t e
wastes at various pH was much f a s t e r with than without
mixing, a t pH 3 with an adsorbent dose of 5 g/L. Iron
removal of 7^ percent was achieved in 3 h with and 18 h
31
without mixing. The dynamics of adsorption of the ions
were calcxiLated and xxsed to design an apparatus and
procedure. The optimal pH is 7 which requires only 2
adsorbers with a diameter of 5 m and a saw dust layer
thickness of 3 m Vs. pH 5 which requires 28 adsorbers with
the same diameter and 1,6 m.
Antimony (III) in small concentration is removed
from wastewater by adsorption on hydroxyl-apatite preci
pitates, (Treshchina et eils, 1983) in the presence of
calcium and phosphate with '-^ 100 percent precipitation
at pH 'N 12.0. The presence of chloride or nitrate at
15-20 mg/L did not interfere but the presence of oxide
and sulphate decreases adsorption of Sb(III) on the
hydroxyl apatite precipitates.
A wastewater containing arsenic is treated with
a titanium compound to fonn titanic acid which forms a
Co- precipitate with aresenic, (Anon 1983). Thus a synthe
tic wastewater pH 2-8 containing 97.08 ug As/ml was
treated with Ti(iso-PrO)^, stirred for 16 h at ^ ° , and
filtered. The filtrate contained 0.025-0.05^ Ug As/ral.
A very similar study was carried out for the
treatment of arsenic containing wastewater. A waste
water containing As is precipitated, oxidized and
treated with an amphoteric metal hydrooxide to remove
32
arsenic. Thus a synthetic wastewater containing
5 ppm As and 20 ppm PO^^ was treated with Fed,,
and the resulting siQ>ematant containing 0.5 ppm As
and 0.9 ppni PO^ was passed through a titanium hydro-
oxide containing column. The effluent contained 5 ppb
aresenic. The titanium hydroxide was prepared by trea
ting Ti0(0H)2 with sulfuric acid, palletizing and neu
tralizing with sodium hydroxide.
Hiroaki et als. (1983) studied on selective
adsorption resins. A macro nuclear chelating resin
(RMH) containing hydrazine groxqjs showed a good
affinity for chromium (III) at pH 5.8-7.5 in batch
e3q)eriments. The adsorption of chromium (III) on the
RMH was not influenced by the presence of Ca over the
concentrations range of 0.01-0.1 mol/L. In the column
method, chromium (III) in an aqueous solution was
favourably adsorbed on the FJMH, when a chromiim nitrate
solution (pH 3.8 and containing either 1 or 10 mg
Cr (III)/L) was passed thro\Agh the column. Chromium
(III) was effectively eluted by passing 20 bed volumes
of 4 mol sodium hydroxide over the resin at a space
velocity of 7.5 h.
The uptake of cadmium (II) and copper (II) from
aqueous solutions at 40° was investigated (Hideki et als,
1983), on slightly soluble hydroxyapatite (HAP), Octa-
calcium phosphate (OCP), and brushite (DCPD). The
33
uptake of M " (ca '*' or Cu "*") proceeded Initially
through an ion exchange reaction Ca "*" 7-^ M"*" and
then through subsequent reactions accompanying the
formation of either Cd-iUCPO^)^.^!^© or, presumably
2+ Ca -dissolving Cu,(P0/^)2»3H20. Exchange fractions of
M"*" were established to be > 10 Cd or > 8 mol percent
Cu "*" for HAP, 2. Cd '*' or 2 9 mol percent Cu " for OCP
and 2 6 mol percent M"*" for DCPD. The reactivity was
in the order HAP < OCP < DCPD, and Cu ' -i9)take occurred
more easily than Cd - iq)take.
Heavy metal ions were removed from solutions
modelling machinery factory wastewaters ixsing coal
as an adsorbent, (Rodionov et als. (1983), Zinc remo
vals of 99 percent were obtained at pH 6 at coal dosages
of 20 g/L, copper (II) and chromium (III) were decreased
to permissible limits at lower pH and adsorbent dosages.
Results were verified with real wastewaters and a scheme
involving 2-stage coal adsorption was developed for
local wastewater treatment.
The reaction of model solutions of chromium
(VI), iron (III), chromium (III) and sulphate with saw
dust was studied by Militsa and Zalesina (1983), to
develop a combined method for treating concentrated
spent solutions from electrolytic chrome plating using
wood wastes. Air-dried sawdust was successfiiL in remo-
3A
ving chromium (YI) at an optimal solid/liquid ratio of
1:8:85 and contact time of 10 mln. in preliminary tests.
The best removals of chromium (VI), chromium (III) and
iron (III) were obtained using saw dust pretreated with
sulphuric acid solution. A 7-stage scheme was developed
for treatment of electroplating wastewater with treated
saw dust.
Frederick et als (1984)reported the removal of
cadmium, copper and lead from wastewaters by 3 algal
species with a concentration factor (CF) on the order
of magnituie of 10^, for zinc, CF is 300-800.
A process was developed to remove CN and COD
(Koichi, 1984), components from metal plating and coati3Tg
wastewater. Cyanide was decomposed with NaClO, and then
residual CN was further removed by precipitation as zinc
cyanide complex. The COD components were removed by
ion exchange, activated carbon, or inorganic adsorbent
but the use of a suitable activated carbon was found
the best.
Low sulphide stockpile leachate was treated in an
unsaturated failing bed to remove trace metals (copper,
nickel, cobalt, zinc), Leachate (28,000 L) passed through
the bed at flow rates of 50-3300 L/day, at pH 6.5-7.1.
Trace metal overall removal was 25 percent, copper 75-90,
35
nickel 23-58, cobalt 3^70 and zinc 12-75 'L
Barbara and Alexander (1984) sxjggested a new
indijstrial wastewater treatment method for the removal
of organic and inorganic contaminants in aqueoi;u5 solxi-
tions by adsorption in a single step, resulting in a
dry, stable sludge.Copper, nickel,zinc, chromium and
iron are removed from a chelated wastewater with 97-100
percent,efficiency.
Hartl et. als (1984) reported the wastewater
treatment for copper, nickel and lead removal by flo-
cculation-sedimentation. The treated wastewater
contains copper, nickel and lead in the amounts < 0.79,
< 1.6 and < 3.4 mg/L, respectively. The metal contents
in the sludge are'^ 50 '/. below the maximum allowed values,
the solid content in the dewatered sludge cake is 60-70 '/.
Ferdinand et.als. (1984) eleminated cyanides in
wastewater, using formaldehyde. Mixing of 2 wastewater
streams, 1 containing cyanide and the other amino acids,
hydroxy acids, and their salts. The reaction rate was
pH dependent and its completeness depended on the CN-
HCHO mol. ratio (R). A complete cyanide removal was
obtained at pH 8-9 and R = 1.5.
Ozonation of electroplating wastewaters containing
OOD 28,200, total organic carbon 6230, chloride 2300,
36
sulphate 720, total nitrogen 3240, nickel(ll) 387, and
other metals 142 mg/L resxilts in an effluent which can
be biologically oxidized with acclimated sludge after
addition of a nutrient solution. The COD was redixed
to 150 mg/L.
Anon (1984) used a strongly magnetic FeO.OH for
treating metal containing wastewaters. Iron (II) in a
solution at pH : 8 is oxidized with air or other oxi
dant, then additional iron (II) and alkaline compound
are added to the solution to pH 7 with further aeration
to prepare FeO-OH-coated magnetite. Wastewater (0.9 L)
containing metal was mixed with 0.7 g magnetite sludge
and 0.1 L water and then stirred at pH 10.5 for 2 h.
No metals were observed in 0.8 L of supernatant. The
magnetite was then regenerated.
Jeffrey (1985) reported the control of heavy
metal discharge in the printed circtiit industry contain
ing copper using NaBH. only, as opposed to NapS20^ and
NaBH. , resulted in lower volumes of sludge which contained
a high copper content (85-95 percent on a dry basis) mak
ing metal recovery completely feasible. Sodium bisulphite
was used prior to NaBH. application when the wastewater
contained ammonium persulfate. The slixige settled
easily, and the effluent contained Cu < 1 mg/L.
37
Toyaki et als. (1985) reported the recovery of
chromium (VI) from wastewater with Iron (H) hydroxide.
Chromium (VI) was selectively recovered containing Cd(ll),
Pb(II), Zn(II), Cu(II) and Cr (III) by adsorption on
iron hydroxide at pH 4,5 and, after separation of the
precipitate, desorption in alkaline solution (pH 10.5).
Phosphate interference was suppressed by increasing the
amount of iron hydroxide and the sulphate interference
was appreciably suppressed by the use of calcium hydroxide
instead of sodium hydroxide as a neutralizing agent.
A thermodynamic analysis of an aq. Hg(II)-Cl~
system showed that decreased chloride concentrations,
are favourable for mercxary removal from the solution by
the neutralizing hydrolysis method. However in the
dilvrte brine from chlor-alkali plant, a certain amount
of free chloride prevents mercury (II) precipitation
and subsequent secondry pollution by Hg-containing salt
sludge .
Showa Denko (1985) reported the removal of
chromium compounds from aqueous electrolytic solutions,
chromium, compounds are adsorbed on iron hydroxide and
removed by filtration.
Walter (1985) proposed a method and apparatus
for removing environmentally unfavourable metal ions from
rinse waters by ion exchange by placing a by pass in the
38
rinse cycle e.g. of an etching apparatus, to feed a
part of the circulating rinsing agent through an ion
exchanger.
Kiyoshi et als (1985) suggested the removal and
recovery of nickel in wastewater from chemical plating
using a strong-base anion-exchange resin (in chloride
form) and a chelate resin (in H form). This method
was proved effective for the removal and recovery of
nickel from the waste rinse water from chemical nickel
plating. The adsorbed nickel on these resins could be
eluted efficiently by 2N hydrochloric acid.
Wastewater containing atleast iron (II) in high
concentration is treated in an oxidation tank with
Fe-oxidizing bacteria, cultivated in highly concentra
ted liquid containing impurities, to oxidize Fe * to
Fe "*", and the generated slvidge containing Fe-oxidizing
bacteria is repeatedly used in the oxidation tank.
(Anon 1985).
Douglas (1985) studied the removal of heavy
metals from wastewater at near neutral pH and without
the addition of large amounts of alkaline chemicals,
by coprecipitation with carrier precipitate precursor
cations (Fe(OH),) and anions (aq. NH,). After preci
pitation, removal by filtration, the cadmium, chromium
39
copper, iron, nickel, lead and zinc concentrations
decreased from 0.6, 2.3, 5, 50, 3.5, 106 and 953
respectively to < 0.1, < 0.1, 1.4, < o.l, 0.2, < 0.5
and 2.8 ppm respectively.
Manfred (1986) suggested the removal of heavy
metals from wastewater by anaerobic biosorption. An
anaerobic sludge-bed reactor removed copper, nickel,
zinc and mercury 99.5, chromium 75, and sulphate
35-40 percent, from vinasse.
Lortie et al (1986) reported the adsorption of
Cr^* on freshly prepared Ti(0H)i . They found that the
temperatiore and ionic strength have little influence on
the adsorption of chromium (III) on titaniiim hydroxide.
Takashi et al. (1986) suggested the treatment of
mercury containing wastewater by reducing Hg ions to
Hg metal, volatilizing the Hg metal with volatile gases,
and cooling to recover the Hg vapor with the gases
recycled for rexise. The recycling of the volatile gases
is effective in preventing Hg diffusion to protect the
environment.
Masao et al. (1986) proposed the treatment method
of dust containing chlorides of heavy metals produced
during melting of flyash, mixed with an alkali metal
40
phosphate in an amount at least equal to that of chlo
rides, melted and solidified. Thus 10 parts dust
(separated from flyash and containing Cd, Pb, Cr , Zn,
Hg, SO^ , CI, Na, K, and Ca) was mixed with 7 parts
Na2HP0^, melted at 600° and solidified. The solid was
completely glassy showed volume decreases 6o percent,
and significantly low elution of heavy metals (Od, Pb,
Cr , Zn, Cu, Hg), and SO^ ~ in leaching test.
Sadhana et al. (1986) extracted chromium (III)
from wastewater in the presence of NaClO^ as a salting
agent, The chromium (III) removal was maximum at a pH
of 2.8 and concentration of Triisoamyl phosphate 30 7
with an initial chromium (III) concentration of 1.5 x
10"^ mol. At Cr(III) concentrations of 0.75-5.0 mg/L,
the removal efficiency was 98.7 percent. The removal
of Cr(III) is significantly affected by the presence of
metals such as Mn(II), Al, and Fe (III).
Licsko and Takaes (1986) reported the removal of
heavy metals in the presence of colloid-stabilizing
organic material and complexing agents. The removal of
heavy metals is improved by Mg addition and adjusting
the pH. The pH that is necessary for destabilizing a
colloid is lowered by increasing the Mg"*" concentration.
The method can be used for the combined removal of
1
different heavy metals (e.g., copper, zinc, cadmium etc.)
In the presence of ammonium salts, some heavy metals
(copper, zinc, nickel) produce stable heavy metal-amine
complexes. The Cu-tetramine complexes formed are stable
and satisfactory heavy metal removal is attained only
at pH 10.5-11.0 since the Mg can only improve the heavy
metal removal to a small degree.
Music (1986) studied the sorption of chromium
( VI) and chromium (III) on aluminium hydroxide. The
factors that influence the sorption of Cr (VI) and
Cr (III) were investigated. The mechanism of sorption
was also interpreted. The best conditions for the
fixation of Cr (VI) and Cr (III) by aluminium hydroxide
are presented.
Makhmetov et al (1986) suggested the method for
removal of arsenic from wastewater by adding a mixture
of V-containing and P-containing slags in a 1:(1-1.5)
ratio as oxidizing and precipitating reagents respectively
and then removing the resultant precipitate.
Tsodikov et al. (1986) stuiied the removal of
lead ions from wastewater, by adding an alkaline earth
metal nitrate and an ammonium salt. The degree of
purification is increased and the procedure is simpli
fied by using ammonium orthophosphate as the ammonium
42
salt at a wt. ratio of lead, alkaline earth metal,
and ammoniim orthophosphate of 1:3-200:3-200. They
have found that stroncium and calcium may be used as
the alkaline earth metal.
Removal of heavy metals from wastewater was
done by mixing an aq. Na aluminate solution with Na^O-
AlpO, mol. ratio > 1, and the heavy metal compounds
precipitated at pH : 7 and are removed from the water
(Volker, 1986).
Shugxii and Guangwei (1987) studied the effective
ness of removing lead, cadmium and chromium from waste
water by water hyacinths. The experiments conducted
were (l) determination of the removal rates of the metals
under different initial concentrations and various pH
values (2) detection of the accumulation and release of
the metals and (3) detection of the removal of lead,
cadmium and chromium from waste-water samples. Water
hyacinths were effective for removing these heavy metals
from wastewater and their effectiveness was in the order
Pb > Cr > Cd. In 6 days, the purification lo^d and the
purification efficiency for Pb, Cd, and Cr were 0.076-
0.496 and 71.21-85.96, 0.008-0.041 and 61.54-83.33, and
0.022-0.056 g/kg (dry wt.)-day and 29.52-58.65 percent
respectively.
43
A similar stxady was carried out by Mario et al.
(1987). The average concentration of silver in dried
material from water hyacinth was 9 ng/g. The plants
were kept for 24 hr in a solution containing 40 mg/L
silver. The silver uptake was 70 percent. The process
can be used for wastewater treatment of Ag-containing
effluents, the water hyacinth used for biogas generation,
and the fermentation residual processed for silver
recovery.
Gudekar and Trivedy (1987) suggested the treatment
of engineering industry waste using water hyacinth.
Refrigeration compressor manufacturing wastewater treat
ment with Sichhomia crassipes resulted in OOD, TSS, and
BOD removal efficiencies of <: 94.15, 9B.07, and 90 percent
respectively. The roots of the E. crassipes contained
maximum concentration of nutrients.
Kalalova et al, (1987) reported the r^aoval of
heavy metals from industrial wastewater. The ammoniation
of ethylene dimethylaerylate-glycidyl methacrylate copo-
lymer gave a macroporus resin (sp. surface area 60 m /g
which is able to complex metals. This resin was-used
as a chemisorbent for the removal of Ag, Cu, Ni, and Zn
from wastewater. In the case of Ag (main pollutant) the
resin had 0,8-1 mmol/g capacity at pH 6.
kk
Schultz et al (1987) stxadied the adsorption and
desorption of metals on ferrihydrite. Metal ions are
removed from dilute solution by sorption onto ferrihydrite
and are then desorbed into a more concentrated solution,
at lower pH, the heavy metals Cu, Pb, Ni, 2n, Cd and
Cr (III) can be quantitatively sorbed from a simulated
plating solution onto ferrihydrite at pH 9.5. Lowering
the pH to 4.5 substantially desorbs the metals.
Krishnan et al (1987) used the natural materials
s\ich as hair and certain plants, which are inexpensive
for the absorption and hence the cleaniip of heavy ele
ments from polluted water was observed. These natural
materials effectively removed the heavy elements concen
tration to the extent of ^ 500. The contact time required
is on the order of several hours. The capacities of
absorption varies from r^ \ to r\j 5 g/kg for mercury and
are lower for arsenic and cadmium. The results show
that with hair, nearly 10,000 L of Hg contaminated water,
a typical output from a 100 ton chior-alkali, plant,
can be treated with >^ 1/2 Kg of hair valued at nJ 25
cents. This makes the process extremely cos-effective
compared to the conventional processes now in use.
Clinoptilolite is an effective sorbent for the
mercury removal from wastewaters in the manufacture of
45
acetic acid (Horvathova and Stefan, 1987), however it
is quickly clogged by colloidal substances and for this
reason, is not suitable for the removal of palladium
from wastewaters in the manufacture of an antioxidant.
Palladium can be adsorbed by clinoptilolite in the abs
ence of colloidal impurities. The following order of
decreasing sorption capacity of clinoptilolite was
obtained : Cs > Pb > Fe > Cu > Zn, Sr, Cd, Al, Co >
Ni > Mn > Cr.
Kenichi et al. (1987) reported the ranoval of heavy
metals from sewage sludge by aeration and extraction with
aq. HNO^ and aq. HCl to remove ^ 75 percent of the copper
zinc, cadmium and lead. Aeration and addition of
hydrogen peroxide increased the efficiency of removal.
Kaiser et al. (1988) suggested the method for the
removal of arsenic from wastewater of the lead glass
industry. Iron (III) in combination with hydrogen peroxide
was used, resulting in an effluent containing < 0.1 mg
As/L. Lead removal by carbondioxide was not affected
with the arsenic removal process.
Slocum et al. (1988) reported the treatment of
metal finishing wastewater with peatmoss contact columns.
Peat moss was effective in the removal of metals and
cyanide. Minimum effluent cyanide concentration was 9.6-
6
12 percent of influent cyanide concentration. Aera
tion of the peat columns increased CN removal capacity
by 27 percent.
Mc-Kay et al. (1988) carried out the sorption
of metal ions by Chitosan. Equilibrium isotherms were
determined of copper (II) and mercury (II) sorption
from aqueous solution by chitosan and kinetics of the
process was studied to evaluate the usefulness of this
material in wastewater treatment.
Mashima et al. (1988) examined the adsorption
of chromium (VI) using a column packed with polyamine
chelating resin. Adsorption of chromixam (VO was 53.6
mg/ml of resin at a Cr(VI) concentration of 100 mg/L,
and 164 mg/ml of resin at a Cr(VI) concentration of
13.3 g/L. Regeneration of resin was achieved by reduc
tion and elution of Cr(VI) with 0.1 percent, hydroxyl-
araine ssLLt aqueous solution at pH 1. Other metal ions
were not eluted.
Henning et al. (1988) studied the removal of
mercury by activated carbon process. The adsorption was
done on activated carbon impregnated with potassium
iodide or sulphuric acid.
Stewart et al. (1988) suggested reverse osmosis
kl
to remove cadmltuB from a metal processing waste stream.
Cd concentration was reduced from I65 to 0.003 mg/L.
Juergen et als (1988) reported the treatment and
recovery of the metals from wastewater. Pb and/or Cu
are selectively recovered from metal processing effluents
containing iron, e.g. wire drawing in a mtdtistage pro
cess comprising precipitation at pH 1.5-2.5 with excess
aq. 10 / sodium sulphide solution, precipitation at pH
3.5-^.5 with 5-10 percent calcixom hydroxide or sodivun
hydroxide and precipitation of remaining Fe ions at pH
8.0-9.5 with NaOH or Ca(OH)p. The precipitates contain
ing Pb and/or Cu are treated to recover the metals.
Diane and Thomas (1988) stiidied the removal of
manganese from aquoxjs industrial waste effluents.
Manganese and/or F and heavy metals are precipitated
from washing effluents from aluminium and tin-coated
steel can manufacturing by the addition of phosphate
in acid medium followed by the addition of Ca in
alkaline medium, where the PO '/Ca "*" ratio is 3:1 to 1:2:5,
at pH 8-9.
Phenols and heavy metals, e.g., Zn, Cu, Cd, Ni,
Pb, Hg, Mn, Cr in a wastewater from ore refining are
removed by mixing with sintered powdered desulfuriza-
tion slag containing Fe oxides 45-48 (Fe basis), CaO
48
and CaS 10-15 (Ca basis), and S compoxmds, 1.5-1.6 */
(S.basis) and then by separating the resulting deposit
from the treated effluent. The resulting supernatant
is discharged. This method is economical to operate.
(Smith 1988).
It appears from the available literature that
several attempts have been made to achieve the separa
tion of 2n (II) from Cd (II) by using different tech
niques, but no work has yet been done and reported on
reversed phase thin layer chromatography (TLC) for the
above mentioned separation. The work presented in this
dissertation describes the chromatographic behavioxor
of some heavy metal ions and their separations. Silica
gel loaded with tributyl amine (TBA) was found to be a
suitable adsorbent for the separation of some toxic metal
ions.
C H A P T E R - III
REVERSED PHASE THIN LAYER CHROMATOGRAPHIC
SEPARATION OF HEAVY METAL IONS ON SILICA
GEL LAYERS LOADED WITH TRIBUTYL AMINE
49
C H A P T E R 3
I N T R O D U C T I O N
The discharge of heavy metals which are non
biodegradable pollutants often contained in the
industrial waste water has been the subject of great
concern in recent years. The heavy metals cause
adverse effects on the living organisms whereas some
are lethal even at very low concentration. Therefore
the presence of sixih substances in water beyond permi
ssible levels may constitute chemical hazard and
render the water unfit for benificial uses. Among
the analytical techniques, the thin layer chromato
graphy is an important tool for the detection and
separation of heavy metals in the field of Environmental
Chemistry.
Description of the Planar Chromatography :
Planar chromatography takes two forms. In thin
layer chromatography, separation takes place on a layer
of a finely divided solid that is fixed on a flat surface.
A sheet or strip of heavy filter paper serves as the
separatory medium for paper chromatography. Thin-layer
chromatography was developed in the late 1950s and by
now has become the more important of the two planer
methods.
50
Thin-layer chromatography provides remarkably
simple and inescpensive means for separating and iden
tifying the components of small samples of complex
inorganic, organic, and biochemical substances. F\jr-
thermore, the methods permit reasonably accurate
quantitative determination of the concentrations of
the components of such mixtures.
General Considerations-.
In planar chromatography, a drop of a solution
containing the sample is introduced at some point on
the planar surface of the stationary phase. After
evaporation of the solvent, the chromatogram is developed
by the flow of a mobile phase (the developer) across the
surface. Movement of the developer is caused by capillary
forces. In ascending development, the motion of the
mobile phase is upward, in radial development, it is
outward from a central spot. Gravity also contributes
to solvent flow in descending development, where move
ment is in a downward direction.
The general principles developed earlier for
column chromatography appear to apply equally well to
paper and thin-layer media. Within these media,
repeated transfer of solute between the stationary and
51
mobile phases occurs. The rate of movement of the solute
depends upon its partition coefficient -
K » C, s/^
It is customary to describe the travel of a particular
solute in terms of its retardation factor R-, which is
defined as
distance of solute motion R >
distance of solvent motion
To compensate for uncontrolled variables, the
distance travelled by a solute is frequently compared
with that for a standard substance under identical con
ditions. The ratio of these distances are designated as
std.
Thin-Layer Chromatography;
Sta t ionary Phase : The so l id absorbents (or sometimos
adsorbents) employed in th in- layer chromatography are
s imi la r in chemical composition and p a r t i c l e s ize to those
of the various types of column chromatography. The most
widely used substances is s i l i c a ge l , which often func
t ions as a support for water or other polar solvents for
p a r t i t i o n chromatography. If, however, the s i l i c a layers
i s oven dried a f te r preparat ion, much of the moisture is
52
lost and the surface becomes a predominately solid one
that serves as an adsorbent for adsorption chromato
graphy.
Thin layer chromatography (TLC) of heavy metal
ions on silica gel (SG) layers offers interesting
possibilities which are greatly enhanced when these
layers are loaded with high molecular weight extrac-
tants. Silica gel retains solutes almost exclusively
on the basis of polarity and thus the separation of
solutes with close polarity even with different molecular
weights is difficult. The selectivity in such cases can
be effected only by varied choice of mobile phases.
Reversed phase-TLC offers some distinct advantages
over normal phase TLC by providing several factors such
as organization of the hydrocarbon ligands on the silica
surface, intercalation of solvent into the bonded layer
and the activity of residual silanols on the solid supp
ort. All these factors influence the selectivity of
the medium in a peculiar manner. Thus, in reversed
phase-TLC the selectivity of a medium can be altered by
varied choice of mobile phases or sorbents, as well as
by surface modifications involving the reaction between
silica support and reactive organo silanes of varying
chain lengths.
53
Because of its simplicity and better resolution
power, reversed phase chromatography has grown to be
a widely used method for chemical analysis of complica
ted mixtures. As a result a ntunber of studies have
been reported on the separation of metal ions using
1-14 various mobile and stationary phases. Most of these
reversed phase studies are based on the use of paper and
column chromatography and little attention has been paid
to the use of TLCp-^'^^,
Separation of Zn(II) from Cd(II) is of great interest
because of close resemblance in their chromatographic
behaviour. Several attempts have been made to achieve
their mutual separation by using normal and reversed
phase paper chromatography^^" , ion exchange chromato-
?? 25 ^U graphy , solvent extraction -^, normal phase TLCr and
25 by precipitation . It is surprising that no work has
been reported on reversed phase TLC for the separation
of Zn(II) from Cd (II). It was therefore decided to
evolve optimum conditions for the separation of 2n(II)
from Cd(II), Ni( II) and Co(II) by reversed phase-TLC
using tributylamine (TBA) as stationary phase on SG
support. Aqueous solvent systems containing variable
concentration of formic acid and sodium formate were
used as mobile phases.
3k
EXPERIMENTAL
^paratus:
A thin layer chromatography apparatus (Toshniwal,
India) for the preparation of silica gel thin layers on
20 X 3 cm glass plates was used. The chromatography
•was performed in 2^ x 6 cm glass oars. Elico pH meter
was used for pH measurements.
Reaj ents :
Silica gel G (BDH)
Tributyl amine (TBA) of Fluka
Sodium formate (SF) and formic acid
(FA) of E. Merck were used.
All other reagents were of analytical grade.
Test Solutions and Detectors:
The 0.1 M solutions of aitrates, chlorides or
sulphates of most of cations were prepared in 0.1 M
?6 solutions of the corresponding acids as described earlier .
Various known volumes of standard solutions of metal ions
were taken to study the effect of loading on the Rp
values. To study the effect of pH of metal solutions
on the Rp value of cations. The pH of the sample solu
tions were brought to the required value by the addition
of either dilute NaOH or dilute HCl.
55
The metal ions were detected by xjsing conventional
spot test reagents.
Metal ions Detectors
VO^*, Cu " , Fe^*, Uol* Potassium ferrocyanide
p + Fe Potassium ferricyanide 4+
Ti Chromotropic acid
Al" Aluminon
^- Pyrogallol
Ni^*, Co^* Dimethyl glyoxime
Zn^*, Cd^*, Mn "*", Cr " Dithizone
Ag*,Bi^"^,Pb^*,Tl"^,Tl^*,Hg^"*" Yellow ammonium sulphide
Ta "*", La "*", Zr^* Alizarine red S
Se Stannous chloride
Th Thoron
Preparation of chromatopiates:
(a) Preparation of Plain SG Thin Layer Plates :
SG was slurried with demineralized water in the
ratio of 1:3 with constant shaking for 5 minutes. The
resulting slurry was coated on clean glass plates with
the help of an applicator to give a layer of 0.25 mm.
The plates were air dried first and then kept at 100° +
56
5°C for 1 h in an electrically controlled oven. The
plates were cooled to room temperatiare by keeping tbem
in a closed chamber before use.
(b) Preparation of TBA Impregnated SG Thin Layers :
Impregnated silica gel thin layers were prepared
by using two methods.
(i) Direct Impregnation Method :
20 gms of silica gel was shaken in a conical
flask with 60 ml of 10-70 percent TBA solution in benzene
(V/v) to obtain a homogeneous slurry. The resultant
slurry was spread over glass plates to form a layer of
uniform thickness {r>^ 0.25 mm). Benzene was allowed to
evaporate at room temperature. The plates were heated
at 100 _+ 5°C for 1 h. and then cooled to room temperature
by keeping in a closed chamber.
(ii) Indirect Impregnation Method :
The plain SG plates were first prepared by adopting
a method as mentioned above and then were impregnated by
placing in chromatographic Jars for development containiiTg
a 10-70 percent TBA solution in benzene (V/V). Benzene
was allowed to evaporate at room temperature and then the
plates were heated at 100°_+ 5°C for 1 h in an electrically
controlled oven. The plates were cooled to room tempera-
57
ture by keeping in a closed chamber and then used
as such.
Solvent SystemsUsed :
(i) Aqueous FA (10"^, 10"^, 0.1, 1.0, 5.0, 10.0,
and 20.0 M)
(ii) Aqueous SF (10"^, 10~^, 0.1, 1.0, 2.0, 5.0 M)
(iii) Mixtures of 1.0 M aq. FA and 1.0 M aq. SF in
8:2, 6:4, 1:1, 4:6 and 2:8 ratio)
Procedure :
The sample solution (3-5 yd) was loaded on plain
or TBA impregnated SG chromoplates with the help of
micropipette. The spots were dried at room temperature
before proceeding for development. The glass Jars cont
aining mobile phase were covered with lids and left for
10 minutes before placing the plates for development.
The plates were developed in a chosen mobile phase by
an ascending technique with a solvent run to 10 cm in
all cases unless otherwise stated. After the develop
ment was over, the plates were air dried and the cations
were detected by spraying appropriate coloring reagents.
The R^ values were calculated from the values of R,
(R^ of leading front and R^ (R^ of trailing front).
58
RESULTS AND DISCUSSION
Results of this study have been sununarized in
figxires 1-4 and tables 1-6,
Reversed phase chromatography on SG impregnated
TBA gave excellent results. The thin layers were of good
quality. However the plates prepared by direct impreg
nation method were found to be better than those obtained
by indirect impregnation method. The time of development
ranged from 1-2 h depending upon the composition of the
mobile phase used. The spots were compact and well
formed in all solvent systems and at all percent impreg-
nations (10-70 percent) of TBA. However, Cd , Ag ,
Hg2* and Hg^* showed some tailing (R -Rj,) > 0.3) in some
solvent systans. The R- values of metal ions were found
to depend \5)on the time and tenperature of drying of
impregnated SG plates. The plates were quite stable in
acidic developers and also in 1.0 M SF but at a higher
pH of mobile phase, the plates were deformed on drying.
As a result, the plates developed in 5.0 M aqueous SF
(pH = 7.75) get deformed on drying. The effect of
various factors on the chromatographic behaviour of metal
ions is given below.
1. Effect of Aqueous SF Concentration on the Mobility
of Metal Ions:
On the basis of chromatographic behaviour on SG
59
layers impregnated with 40 percent TBA in varying con
centrations of SF (O.OOl to 5.0 M), the metal ions
can be classified into the following groups :
(i) Metal ions such as \J0^^*, Fe^*, Al "*", Ag*, Pb " ,
Bi" , Tl^ and Ti did not show any mobility over the
entire range of SF concentrations. The low R- value
for these metal ions may be attributed to the formation
of anionic/neutral complexes with SF similar to those
reported by Qureshi et al for few cations. Hg^ and
Hg produced tailed spots starting from the point of
application.
(ii) Ni and Co moved with the solvent front giving
high R„ (/->.J0.9) over the whole concentration range.
The absence of sorption in these cases may be attributed
to the lack of formation of anionic metal formate
complexes.
(iii) Metal ions like Tl and Cd' ' showed an increase
in mobility with the increase in SF concentration giving
R^ equal to 0.9 in 5 M SF. The increase in R- value
with the increase in SF concentration may be probably
due to increased complexation at higher pH.
(iv) Cu "*" and Zn "*" did not move in solvents containing
upto 1.0 M SF. However a sudden increase in their R-
values in 2.0 M and 5.0 M SF was observed.
60
All the metal ions were detected satisfactorily
at all SF concentrations (0.001-5.0 M). The development
time increases with the increase in molar concentration
of SF until it reaches to 2 h in 5.0 M SF.
2. Effect of FA concentration on the Mobility of
Metal ions:
The study of chromatographic behaviour of metal
ions on ^0 percent TBA impregnated SG plates in acidic
developers containing varying molar concentrations of
aqueous FA (0.001-20.0 M) gave some interesting results.
The main points emerged out of this stixiy are as follows ;
(i) Hgp^ formed elongated spots at all FA concentra
tions while Bi "*" and Cd produced tailed spots (starting
from the origin) in 5-20 M and 0.001 M - 0.1 M FA respec
tively.
(ii) Ag"*", Pb "*" and Ti " remained at the point of
application at all FA concentrations losed. Conversely,
2+ 2 + Ni and Co moved with the solvent front probably due
to the solvation of these ions/complexes by the mobile
phase.
(iii) Uo|"*", Fe "*", Al "", Bi " , Zn - , Cr "", Cu^^ and Cd ""
did not move in mobile phases containing upto 0.1 M FA.
On further increase in acid concentrations these metal
61
ions show significant mobility giving R- 0.7-0.9 in
1.0 M FA. The R- values reach a maxiniiin (R^ = l.O)
at higher FA concentrations (i.e. 5-20 M). The higher
FA concentration was found unsuitable because of (i)
spreading of spots (ii) greater development time
(iii) less sharp detection of most of the metal ions.
The increase in R^ with increase in molar concen
tration of FA is attributed to the increase in the
number of H^ ions competing with the cations/or cationic
complexes, for the exchange sites.
3. Effect of TBA Impregnation on the Mobility of
Metal ions -.
Fig. 1 shows that TBA impregnated SG layers are
more strongly sorbing than unimpregnated or plain SG
layers for most of the metal ions as indicated by posi
tive values of AR-.. Here AR- is the measure of the
difference in the R« values of metal ions on unimpreg
nated and impregnated SG layers i.e. AR- = R^ on unim
pregnated SG layers- R» on impregnated SG layers. Thus,
TBA impregnation enhances the selectivity of the plain
SG layers.
Fig. 2 shows the effect of degree of impregnation
of TBA on the R^ values of metal ions in 1.0 M FA and
in 1.0 M FA + 1.0 M SF (2:8) solvent systems. The R^
62
--• 1-OM SF
-® l-OMSF + 1 OM FA (1:1)
+ 1-0 r
-y. 1-OM FA
-A O lM FA
< > O U . U . O Z O N < O X X | - » - Q . C D I D I -
cations
F i g . l :
Comparison of selectivitles of TBA^lmpregnated
and tminqpregnated silica gel layers in different
solvent systems.
63
values for only those cations which gave compact spots
were taken for plotting the figxires. It is evident
from fig. (2) that in 1.0 M FA, the R^ values generally
decrease with the increase in degree of impregnation.
However, Cd and Bi-"*" showed constancy in R- values at
2+ all degrees of impregnation. 2n showed significant
tailing (R^ » 0.0-0.6), over 10-20 percent impregnation.
In solvent system containing the mixture of 1.0 M
FA and 1.0 M SF in 2:8 ratio, the plots (fig. 2) showed
frequent fluctuations over the entire range of TBA impreg
nation. Interestingly, a few cations showed stronger
sorption at 30 percent TBA impregnation. Detection of
all metal ions were very clean and sharp at all degrees
of impregnation but the spots were more compact at higher
degrees of impregnation. The shapes of these curves can
be tentatively explained on the basis of the existence of
a neutral, positive, or negative species as well as the
possibility of formation of less adsorbed higher charged
negative complexes. Some other phenomena such as the
adsorption in the network of the support, precipitation
in the network of the support, precipitation, hydrolysis
and solvent solvent interactions, may play an important
role to effect the sorption behaviour of metal ions on
impregnated SG layers.
1-0
0-8
j 0-6
Rf 0-6
0-2
0-0
2+ Cd
-I 1 I 1 I I I
10 20 30 60 50 60 70 Vo impregnation wi th TBA
I I 1 ! I 1 i -
- O -
- ® -
Zn 2 +
J ! 1 I 1 1 L.
- O -
^o«..
Ni •2 +
J I 1 L 10 20 30 40 50 60 70 % impregnation wi th TBA
Fig . 2a and 2b :
P l o t of R^ Vs. pe r cen t age impregnation of TBA in benzene^
8 '& 1.0 M FA G 0 1.0 M FA + 1.0 M SF (2 :8 )
65
1.0 r
0 8
' O.G
Rf 0.^
0-2
00
10
0-8 \-
" 0.6
Rf 0.6 -
0-2 -
0-0
1-0 r
0-8
0-6 H
Rf 0.4
0.2 h
0-0
1.0
0 8
0-6
Rf 0.4
0-2 h
0-0
Co' 2 +
Mn 2 +
O-- - O - O — - O
Tl 3 +
O , . '^o-^~^^^^.-^-o
Pb 2 +
-C t ^ -^--^-.^^^ 10 20 30 40 50 60 70
Vo impregnadon with TBA
J3—0-O iD -
- O ' '<y
Bi 3 +
- ^ - O — - r r r - - ^ Q - - O
- - 0 -
Tl
1 1
2 + Hg
1 1
o
1 1
10 20 30 40 50 60 70 Vo impregnation with TBA
2b
66
4. Effect of Mixed Solvent Systems Containing Mixture
of 1.0 M FA and 1.0 M SF on the Mobility of Metal
Ions :
It is clear from Fig. 3a that 1.0 M SF is the
best solvent for the separation of Zrr'^ from Cd , Ni "*"
2 + and Co on 60 percent TBA impregnated SG layers. Though
7+ ? +
the separation of Cd from Zrr in this solvent is also
possible on UO percent impregnated plates but the higher
tailing of Cd decreases the resolution of its separa
tion from Zn^* (Fig. 3b). It is clear from Fig. 3b that
1.0 M SF behaved differently than 1.0 M FA as a mobile
phase. Most of the cations move faster in FA and produce 2+ 2 + more compact spots compared to SF. Ni and Co showed
identical behaviour in both the solvent systems and
moved with the solvent front. Figs. 3c-d summarize the
chromatographic behaviour of metal ions in solvent systems
containing mixtures of 1.0 M FA ani 1,0 M SF in different
molar ratios. It is evident from these curves that most
of the metal ions showed relatively greater mobility and
higher compactness in solvents containing higher percen
tage of FA.
5. Sffect of pH of Metal Solutions on the separation
of Zn " from Ni " , Co " and Cd "*";
It is clear from Fig. that the R- values of
67
R 0 6
l O M SF
A = 1 0 M SF B = 1-0M FA
(C ) A=1-0M SF + lOM FA{8
8=1-0M SF + 1 0 M F A ( 2
C = 1-0M SF + 1-OM FA(1
2) 8) 1)
A = 1 0 M SF + VOM FA(6:A)
B=1-0M S F + l O M FA(/i-6)
— l_ 4( » o — ^ C 0> Tj 0> W» m ,0 .—
< > o u . u . o 2 o r N 4 < o x i f l p a . C D r ) » : i cations
Fig. 3 : Plot of R- Vs metal ions in different solvent systems
a - 60 '/ TBA impregnated silica gel layers.
b,c,d = 40 •/ TBA Impregnated silica gel layers.
• • compact spots; A A Tailed spots with
0- -G Tailed spots with RT-R^P < 0.4.
68
1-0
0-8
0-6
Rf 0-A
0-2
O'O 0
Cd ,'*' Ni ' ^ond Co^"^
1 2 3 ii pH of metal solutions
Fig. 4 :-
Plot of pH of metal solxitions Vs R^ on silica
gel layers impregnated with 60 •/ TBA in solvent
system containing 1.0 M sodium formate and 1..0 M
formic acid in an 8:2 ratio.
69
Zn "*", Ni " , Co "*" and Cd "*" are independent of the pH
of the sample solution in the pH range of 1-5. Thus
2 + a good separation of Zn from these metal ions can be
obtained on 60 percent TBA impregnated SG layers in
mobile phase containing a mixture of 1.0 M SF and 1.0 M
FA in 8:2 by using unbxiffered sample solutions without
adhering to the close control of the sample pH.
The enhancement in the selectivity of SG layers on
impregnation with TBA provides an opportunity in achiev
ing many analytically important separations. Many such
separations have been actually realized and have been
2+ tabulated in tables 1-4. The separations such as Zn -
Cd 2*, Al5*-Cu2\ VD2•^-Tl5^ ^0^^.^\ Th'^^-Zr'^^ Fe^*-
Tl5^ Al5^-Cu2*-Ni2*-Ti^^ Cr^^-Bi5*-Cd2'^-Co2^ Zn - -Cd " -
Pb " and Zn2"*"-Tl* -Pb "*" are worth mentioning.
Table 5 summarizes the results of the effect of
loading on the R- values and the lowest possible detec
table amount of metal ions on the chromatopiates. It
is evident that TBA impregnated SG layers gave highly
compact spots over a wide range of loading amount of
the metal ions. 0.5 pg of Ni gave R„ equal to 0.9^
while it is 1.0 for 400 ug of Ni "*".
In order to bring out a more clear picture
regarding the separation of Zn "*" from Cd "*", Ni "*", and
70
Co , some TLC parameters such as AR- (R^ of separating
metal ion-R- of Zn ), separation factor (a) and reso
lution (Rs) have been calcialated. These data have been
presented in table 6. The values for a and Rs have been
calculated by using the following relationships.
(M » separating metal) ( i ) a = KZn/Kj^
/ 1 - R-
/ where K is a capacity factor which measures the degree
of retention of a solute compared to the solvent.
R : s 1/2 (d- -Hi2)
where AX is the distance between the centres of spots
and d-. , d„ are their respective diameters. Two solutes
are just separated if Rs is equal to 1. It is clear
from table 6 that a good separation of Zn from Cd ,
Ni and Co can be carried out by using the proposed
method. The AR- value is always greater than 0.5.
A high value of separation factor and well resolved
spots with R_ >, 5 are the added advantages of this
study.
The proposed method consisting the use of 40-50"/
TBA impregnated SG layer and a mixture of 1.0 M SF and
71
1.0 M FA in 8:2 ratio as developer is very reliable and
reproducible for achieving the separation of a particular
cation from others in general. It is particularly more
usefiiL if one needed sharper and clearer ternary and
quarteraary separations. The spots are so well formed
and compact that good quartemary separations are always
possible. It is a very reliable method to separate Zn
from over a reasonable pH range of sample solutions.
72
+> c 0) o t l 0) o,
s A •P •H
TJ 0)
-P CO
c bO 0)
^
ra t Q) >, CO -3
rH
a)
CO o •H f H •H CO
C O
n 0) >
•H Si o <
to C o •H
• P CO U CO a Q) CO
>> U CO c •H OQ
• »
CO rH
0) H X> CO H
• 0} 0 0) P (0 > . CO
p C (U > H O
CO
P C 0) ^ (D M M •H a c •H
< 03 H
,»-v
oT 1
cr: •^-^
•o ^ > 0)
:d <
CO
o •H P CO
CO a 0) to
CO
a <D p CO
CO
p
CD >
rH O
CO 1
» ^ t^
« o
• o
v_x
4-K>>
^
(< O
o o 1 o
• o
+ ^
•H
1
ir> (H
• o 1
K>i
O
+ fM
O >
s:
o • H
^ - N
00 •
o 1
o • H
N.^'
+ CM
•H 2
tu o
o o 1 o
• o
+ ^
1
i n H
• o
1 r O
+ cv
^
o o 1
o •
o
+ <r •H
EH
1
i n •
o 1
vO
O
+ K^
^
o o 1 o
• o
+ 4-
1
i n •
o 1
t ^
o
+ K>
(U
c o 1
cr> •
o
+ eg
•H 2
1
O •
o 1
o o
+ J-
•H
>^-s OvJ
•
o 1 i n
• o
\—y
+ CM P >
U o
o o 1 o
• o
+ -d-
•H EH
1
vO •
o cA o
+ cvyvj
+ CM
O O
+ CM
•H 2 :
<H
o CO
o ^
•H
a 1
o •
o 1
o o
+ f<^
Ct4 CO
s o • rH
< ^ o
• o 1
H • o
V . X
+ »n
0) tL,
u o
, -x CM
• O
1 K^
• o ^ ^
+ ^ 3 o
t
00 •
o 1
o rH
+ CM
^-^ O
• o 1 in
o •
o v--*
- » •
CM C N
U o
^'^ o
•
o 1
H •
o
+ rn
•H CQ
1
00 •
O »
o rH
+ CM
^
1
73
KN
H a:
1 • J
oc
n 0) > 0)
:d o <:
C o •H + CO u ca o, 0) t o
/ " • ^
t ^ •
o cA o
+ C\J o o
1
,--> CO CM
• o 1 i n CM
• o
• o (A
• o
+ CM
o u o
^^s vO CM •
o 1
K>
o
+ f ^ w
:3 o
1
^ - N
H •
O 1
CM •
O
^ • v
cn •
o 1
o H
+ CM •H
z 1
^ - x H
• O 1
CM
O
y - ^
vD •^
• O
a!,
o
- » •
CM
s 1
(• '-^ c>-H
• O
cA CM
O
, — N
o •
o 1
o o
+ 4-
1
, . ^ k
K^ ^f^
• O
1 vO K>
O
o 1
i n
• o
+ i n
CO
o /• ^ CM
• o 1
CM ^
o
+ K^
• o 1
i n CM •
o
> - •
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C H A P T E R - IV
USE OF ACIDIFIED SILICA GEL LAYERS AS AN
ADSORBENT IN CHROMATOGRAPHIC SEPARATION
OF SOME METAL IONS
83
C H A P T E R IV
INTRODUCTION
In c o n t i n u a t i o n of oxxr p rev ious work ^ ,
we have used ca rboxy l i c and mineral ac ids as impre-
gnants on s i l i c a ge l l a y e r s in o rde r t o unders tand t h e
r e t e n t i o n behaviour of some metal i o n s . As a r e s u l t
we have achieved some important s e p a r a t i o n s which a r e
d i s cus sed i n t h i s c h a p t e r . However, some more work
i s r e q u i r e d t o pu t t h e s e r e s u l t s fo r more p r a c t i c a l use .
In t h i s d i r e c t i o n , t h e q u a n t i t a t i v e s e p a r a t i o n of
d i f f e r e n t va lence s t a t e s of mercury i s i n p r o g r e s s .
The s e p a r a t i o n of Hg(II) from some metal ions on t h i n
l a y e r s of s y n t h e t i c i no rgan ic ion exchangers has been
31-36 e a r l i e r a t tempted by some workers-'^ -^ .
However t h e i r s t u d i e s s u f f e r t he fol lowing
l i m i t a t i o n s .
( i ) Effec t of anions on t h e s e p a r a t i o n of m e r c u r y ( l l )
from o t h e r ions has no t been examined.
( i i ) Loading e f f e c t of s e p a r a t i n g ions has no t been
s t u d i e d .
Therefore i t was thoughtworthwhile t o op t imize
t h e c o n d i t i o n for t h e s e p a r a t i o n of mercury ( I I ) from
s e v e r a l metal ions
&k
EXPERIMENTAL
Apparatus
Toshniwal TLC apparatus was used for the p re -
paucation of s i l i c a gel l aye r s .
Reagents
Silica gel G of BDH India and all other reagents
were of analytical grade.
Impregnants
Following aqueous impregnants whose concentra
tions are given in parenthesis were used.
(i) Oxalic acid (0,1, 0.5, 1.0, 2.0 and 10 /)
(ii) Citric acid (0.5 '/)
(iii) Tartaric acid (0.5 /)
(iv) Formic acid (0.5, 1.0, and 2.0 'A)
(v) Hydrochloric acid (O.l, 2.0, 5.0 and 10 '/)
(vi) Nitric acid (2.0 /)
(vii) Perchloric acid(2.0 and 5.0 "/)
Solvent Systems Used
The solvent systems used are given below.
85
Solvent System Composition EA-Acetone-FA-Water
10
8
7
2 : 1
6 : 1
8
10 : 1
k : 1
Preparation of silica gel plates:
Plain silica gel thin layers were prepared as
discussed earlier. For the preparation of acid impreg
nated silica gel layers 20 gram of silica gel was
shaken in a conical flask with 60 ml of 0.1-10 /. aqueous
solutions of various acids to obtain a homogeneous slurry.
The resultant slurry was spread over glass plates to
form a layers of uniform thickness ('~ 0.25 mm). The
plates were heated at 100 ± 5°C for 1 h, and then
cooled to room temperature by keeping in a closed
chamber.
Test Solutions and Detectors ;
Test solutions and detectors used were the same
as earlier.
86
Procedure
Plates were developed xjsing ascending technique
as discussed earlier and the ascent was kept 10 cm in
all cases.
RESULTS AND DISCUSSIONS
The results obtained have been shown in figs.
5-7 and tables 7-10. The silica gel layers impregna
ted with carboxylic and mineral acids provide some
new separations. Silica gel layers impregnated with
acids were found more selective to most of the metal
ions compared to plain silica gel layers. The R^
value of metal ions remained almost constant in the
range of 0.1 - 2 / oxalic acid impregnation. It is
evident from fig. 5 that oxalic acid impregnated
silica gel layers retained the metal ions more
strongly than the plain silica gel layers. Cr, Mn
and V are only the exceptions which showed strong
adsorption on plain silica gel layers. The chromato
graphic behaviour of metal ions on mineral acids and
carboxylic acids impregnated silica gel layers have
been summarized in fig. 6(a) and (b). The mobility
of the most of the cations was higher in formic acid
impregnated plates compared to oxalic acid impregnated
plates (fig. 6b) showing the stronger complexing
87
< I— ^c:>5^ii 11 o 2 < I M 2 O > - X I—»— < } — > o 2 : i j L U . o 2 o f ^ 2 o > X I—»—
Metal ions »
Fig. 5 :
Plot of AR^ (R^ on plain silica gel layers
Rf on Impregnated layers) Vs metal ions.
88
a)
'mpregnants:
o 2 / HCI
X 2 / HGO^
A 2/ HNO3
. 5/ HCIO,
(b)
< P > o l l 2 £ S z 5 . 5 M ^ S ^ f ^ x P f e ^ ^ 3
o 2/ FA
® 2 / Ox Ac
Metal ions
Fig. 6(a) and (b)
Mobility of metal ions on mineral acid and carboxylic acids impregnated s i l i c a gel l aye r s in ethyl ace ta t e -acetone-formic acid-water so lvent system.
89
tendency of oxalic acid. Amongst the mineral acids(Fig.7)
xjsed, perchloric acid and hydrochloric acid were found
better impregnants. The optimiam impregnant concentra
tion was found to be 5 percent for HCl or HCIO^ and
2 percent for oxalic acid. Almost all the cations
tailed on silica gel layers impregnated with 0.5 'A
oxalic acid, citric acid or tartaric acid. 5 percent
perchloric acid impregnated silica gel layers gave
more compact spots compared to 5 percent hydrochloric
acid impregnated plates. Ni "*", Cd^*, Zn "*" and Fe^*
tailed at all HCl concentrations (O.l - 10 percent).
Th " , Bi^*, Ag*, Pb " , Tl"*" , remained at the point of
application, while Cu " , Uo|*, Fe moved with the
solvent system at all HCl concentrations. However,
the R- of Co increases with the HCl concentrations.
The substitution of water by 1.0 M aqueous sodium
formate solution in solvent system leads to the
formation of tailed spots for most of cations. The
R- values of cations were found to be dependent on
the concentration ( /. volume) of formic acid or water.
Several important separations achieved on acid
impregnated silica gel layers have been summarized in
tables 7-lC.
The separation of Hg "*" from Hg " and of Th "
from UOp using 2 percent oxalic acid and 5 percent
perchloric acid as impregnants respectively was carried
90
© ® 5 •/ HCl
O O 5 •/ HCIO^
C E ^. -J C t- 0>-r3-^*CTib>+ X5—r-—, (- ±: 0; a* ovz . 3 ^ ' . < ^r>02:LL l i_oZ O MM
Metal ions
Fig. 7 Comparison of hydrochloric acid and perchloric acid
as impregnant on the mobility of cations in ethyl
acetate-acetone-formic acid-water solvent system.
91
2- — -out in the presence of certain anions. OOt , BrO,, I ,
lor, Br", NO2, NOl, CI"", Cr^Orj^'f and CrO^" do not hurt
the above separations. The A R^ values for Hg - Hg^
4+ 2-f and Th - UOp separations were found to be 0.85 and
0.68 respectively. The loading effect of separating
metal ions has also been studied and the separation
of 10 yig of Hg(ll) fromlmgof Cu(II), 1 mg of Ni(ll),
10 mg of Pb(II) and 50 yg of Hg(I) has been successfully
achieved.
Apart from the qualitative separations, the second
aspect of this problem is the quantitative separation
of Hg(II) from other metal ions such as copper (II),
nickel (II), lead (II) and mercury (I). The quanti
tative separation of mercuric ion from mercurous ion
is important from analytical as well as theoretical
point of view.
It is also aimed to apply the method developed
for the quantitative separation of mercury (II) on
industrial wastes containing mercuric salts.
92
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94
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97
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C H A P T E R - V
S U M M A R Y
98
C H A P T E R V
S U M M A R Y
This d i s s e r t a t i o n e n t i t l e d , Studies on the Disposal
and Treatment of some Indi is t r ia l Wastes, mainly com
pr ises of four chap te rs . The f i r s t chapter i s the
introductory par t giving a general idea regarding
environmental po l lu t ion and nature and cha rac t e r i s t i c s
of i ndus t r i a l eff luent which plays a important ro l e in
degrading the qual i ty of the environment. As the rapid
i ndus t r i a l i za t i on i s taking p lace , there has been an
appreciable increase in the volume of the indus t r i a l
e f f luents , containing several tox ic substances and
often heavy metals which causes an adverse effect on
aquatic l i f e when dischairged in to the water body.
Relevant to t h i s subjec t , in the second chapter,
a de ta i led and upto date l i t e r a t u r e on the treatment
and disposal of i ndus t r i a l wastes, has been reviewed.
In addi t ion, the d i f fe ren t methods for the ranoval
and recovery of heavy metals from indus t r i a l effluents
have also been described. Among the ana ly t ica l tech
niques used for the de tec t ion and separation of heavy
metals (qua l i t a t i ve and quant i ta t ive) the th in layer
chromatographic method has been found to be much more
accurate , r e l i a b l e and inexpensive. This method i s
99
foxmd to be very sensitive even upto the microgram
quantity. Therefore, it was thought to optimize the
different conditions adopting thin layer chromatogra
phic method using silica gel as an adsorbent,by preparing
a synthetic industrial waste containing toxic metal
ions and finally to apply the optimized method on
wastes from different industries.
The third chapter deals with the study of thin
layer chromatographic separation of heavy metal ions
on silica gel layers loaded with tributylamine. The
chromatographic behaviour of some heavy metal ions has
been stixiied in formic acid sodium formate system.
Several important binary,ternary and quarternary sepa
rations have been achieved. The separations such as
2n2*-Cd2^ Al5-^-Cu2*, YO^^-Tl^^ VO^^-W ^t Th -Zr" "-
Fe5^-Tl5% Al5^-Cu2*-Ni2-^-Ti'^\ Cr5^-Bi5•^-Cd2^-Co2^
Zn '*"-Cd ' -Pb ' , and Zn^^-Tl"^ -Pb "*" are very important
from theoretical as well as analytical point of view.
The effect of various factors such as (i)varying
concentration of aqueous sodium formate (.001 to 5.0 M),
(ii) Varying molar concentration of aqueous formic acid.
(.CC1-2C.0 M), (lii) percent impregnation of trlbuty-
lamine (10-70 / ) , (iv) mixed solvent systems containing
mixture of 1.0 M formic acid and 1.0 M soidium formate,
, (v) pH of metal solutions, (vi) and loading amount
of metal ions were studied on the mobility of metal ions.
The lower detectability level of some of the metal ions
100
playing an important roie in water quality is foimd
Cu "" (1.0 ^ ) , Ni^^ (0.5 pg), Co^* (10.0 pg), Zn^*
(0.3 ys)f and for Cd (l.O pg). Hence the proposed
method consisting the vse of -60 percent TBA impre
gnated silica gel layers and a mixture of 1.0 M
sodium formate and 1.0 M formic acid in 8:2 ratio as
developer is very reliable and reproducible for achi
eving the separation of a perticular cation from others
in general.
In the last chapter a comparative study of plain
and acids impregnated silica gel layers towards the
adsorption of some metal ions was carried out and some
new separations were achieved. It was found that acid
impregnated silica gel layers were more selective for
most of the metal ions compared to plain silica gel
layers. Oxalic acid impregnated layers retained the
metal ions more strongly. Amongst the mineral acids
used, hydrochloric and perchloric acids were found
better impregnants. Concentrations of carboxylic and
mineral acids as impregnants were established.
R E F E R E N C E S
101
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lOA
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P 3593 F
Joiipiial of Planar Chromatograpliy —Modern TLC
DYNORPHIN (1-10)/SORBITOL IN SIMS BLOT nj/2 ,235
m/z 12 36 [] tlf'-'
.:^~,'
Secondary ion mass spectrometry in imaging analysis. See page 738
2/88 A Publication of iQj H t t t M g
Reversed Phase Thin Layer Chromatographic Separation of Heavy Metal Ions on Silica Gel Layers Loaded with Tributylamine
Mohammad Ajmal*, A. Mohammad, N. Fatima, and Akhtar H. Khan
Key Words:
Thin layer chromatography, TLC Heavy metal ions Tributylamine loaded silica Reversed phase
Summary
Chromatographic behavior of some heavy metal Ions on silica gel layers loaded with tritrntylamine has been studied in formic acid-sodium formate systems. Several important binary, ternary and quartemary separations have t>een achieved. Zn has t>een successfully separated from Cd, Ni, and Co. Some TLC parameters for Zn-Cd, Zn-Ni and Zn-Co separations have also t>een calculated.
1 Introduction
The discharge of heavy metals, which are nondegradable pollutants often contained in industrial waste water, has been the subject of great concern in recent years. Heavy metals cause adverse effects on living organisms, and some are lethal even at very low concentration. Therefore, the presence of such substance in water beyond permissible levels may constitute a chemical hazard and render the water unfit for many uses. Among the analytical techniques available, thin layer chromatography is an important tool for detection and separation of heavy metals in the field of environmental chemistry.
Reversed phase TLC offers some distinct advantages over normal phase TLC by providing several special features, such as organization of the hydrocarbon ligands on the silica surface, intercalation of solvent into the bonded layer, and the activity of residual silanois on the solid support. All these factors influence the selectivity of the medium in a specific manner. Thus, in reversed phase TLC the selectivity of a medium can be altered by varying the mobile phases or sor-bents, as well as by surface modifications involving reaction between silica support and reactive organosilanes of varying chain lengths.
Because of its simplicity and better resolution power, reversed phase chromatography has become a widely used method for chemical analysis of complicated mixtures. As a
M. Ajmal, A. Mohammad, N. Fatima, A. H Khan, Environmental Research Laboratory, Department of Applied Chemistry, Z H. College of Engg. and Technology, Aligarti Muslim University, Aligarh 202 002. India
result, a number of studies have been reported on the separation of metal ions using various mobile and slationary phases [1-14]. Most of these reversed phase studies are based on the use of paper and column chromatography and little attention has been paid to the use of TLC [15-1^ .
Separation of Zn(ll) from Cd(ll) is of great interest because of close resemblance in their chromatographic behavior. Several attempts have been made to achieve their mutual separation by using normal and reversed phase paper chromatography [19-21], ion exchange chromatography (22), solvent extraction [23), normal phase TLC [24], and by precipitation [25]. It is surprising that no work has been reported on reversed phase TLC for the separation of Zn(ll) from Cd(ll). It was therefore decided to establish optimum conditions for the separation of Zn(ll) from Cd(ll), Ni(ll), and Co(ll) by reversed phase TLC using tributylamine (TBA) as stationary phase on a silica gel (SG) support. Aqueous solvent systems containing variable concentrations of fonnic acid and sodium formate were used as mobile phases.
2 Experimental
2.1 Apparatus
A thin layer chromatography apparatus (Toshniwal, India) for the preparation of silica gel thin layers on 20 x 3 cm glass plates was used. Chromatography was performed in 24 x 6 cm glass jars. An Elico pH meter was used for pH measurements.
2.2 Reagents
Silica gel G from BDH, TBA from Fluka, sodium formate (SF) and formic acid (FA) from E. Merck (India) were used. All other reagents were of analytical grade.
2.3 Test Solutions and Detectors
The 0,1 M solutions of nitrates, chlorides, or sulfates of most of cations were prepared in 0.1 M solutions of the corresponding acids. Various known volumes of standard solu-
128 Journal of Planar Chromatography 1988 Dr. Alfred Huethig PuDlis^ers
RP-TLC o' Heavy Mel.il Ions
tions of metal ions were taken to study the effect of loading on tfie flf values. To study tfie effect of pH of metal solutions on the R, value of cations, the pH of the sample solutions were brought to the required value by the addition of either dilute NaOH or dilute HCI. Zn^' and Cd^* were detected with difhizone solution and other metal ions were detected by using conventional spot test reagents [26].
2.4 Preparation of Chromatoplates
2.4.1 Preparation of Plain SG Thin Layer Plates
SG was slurried with demineralized water in the ratio of 1:3 with constant shaking for 5 minutes. The resulting slurry was coated on clean glass plates with the help of an applicator to give a layer of 0.25 mm. The plates were air dried first and then kept at 100°±5''C for 1 h in an electrically controlled oven. Tlie plates were cooled to room temperature in a closed chamber before use.
2.4.2 Preparation of TBA Impregnated SG Thin Layers
Impregnated silica gel thin layers were prepared by two methods.
Direct Impregnation Method: 20 g of silica gel was shaken in a conical flask with 60 ml of 10-70% TBA solution in benzene (V/V) to obtain a homogeneous slurry. The resultant slurry was spread over glass plates to form a layer of uniform thickness (= 0.25 mm). Benzene was allowed to evaporate at room temperature. The plates were heated at 100 ± 5°C for 1 h and then cooled to room temperature in a closed chamtjer.
Indirect Impregnation Method: The plain SG plates were first prepared by adopting a method as mentioned above and then were impregnated by placing them in chromatographic jars for development containing a 10-70% TBA solution in benzene (V/V). Benzene was allowed to evaporate at room temperature and then the plates were heated at 100°± 5°C for 1 h in an electrically controlled oven. The plates were cooled to room temperature in a closed chamtjer and then used as such.
2.5 Solvent Systems Used
Aqueous FA(10"^ 10-^ 0.1. 1.0, 5.0. 10.0, and 20.0 M) Aqueous SF (10"^, 10-^ 0.1, 1.0, 2.0, 5.0 M) Mixtures of 1.0 M aq. FA and 1.0 M aq. SF (8:2, 6:4, 1:1, 4:6. and 2:8 ratio)
(0 (ii) (iii)
2.6 Procedure
The sample solution (3-5 MO was loaded on plain or TBA impregnated SG chromatoplates with the help of micropi-pettes. The spots were dried at room temperature t)efore development. The glass jars containing mobile phase were covered with lids and left for 10 minutes before introducing tfie plates for development. The plates were developed in the chosen mobile phase by the ascending technique with a solvent run to 10 cm in all cases, unless othenwise stated. After
development, the plates were air dried and the cations were detected by spraying appropnate coloring reagents The R, values were calculated from the values of R, (ft. ot leading front) and fly {Rt of trailing front).
3 Results and Discussion
The results of this study are summarized in Figures 1-4 and
Tables 1-6.
Table 1
Binary separations achieved on silica gel layers impregnated with 40% TBA in different solvent systems.
Solvent system Separations achieved {R^ - Rj)
1.0 M FA V(y-(0.3-0.15)-Ti'''(0.0-0.0) or Ap-(0.8-0.7) V(y*(0.3-0.15)-W*-(0.0-0.0) or Np-(1.0-0.8) AP'(0.6-0.5)-Ti*-(0.0-0.0) Fe'-(0.7-0.5)-Ti'-(0.0-0.0) Ti'*(0.0-0.0)-Ni^-(0.9-0.7) UOi*{0.8-0.6)-Ti"(0.0-0.0) or VO'*(0.35-0.2) Fe^*(0.0-0.0)-mixtures of Ni^'. Co'' Mn'-(1.0-0.8)-Cu="(0.3-0.2) or Fe'-(0.1-0.0) Mn^'(1.0-0.8y-Bi''(0.1-0.0) or Zn'-(0 05-0.0) UOf(0.25-0.22)-Co'-(0.8-0.7) Ap-(0.2-0.1)-Cu'-(0.3-0.26) or Cd'-(0.8-0.7) Ap-(0.2-0.1 )-Ni'-{ 1.0-0.9) Zn'*(0.28-0.17)-Cd'-(0.8-0.66) UO|-(0.36-0.33)-Zr^-(0.0-0.0) Ti''*(0.0-0.0)-Ap-(0.42-0.2) or Ta**(0.45-0.3) Se'-(1.0-0.9)-Pb'* or Bi '(O.O-O.O) Se'-(1.0-0.9)-Ti**(0.0-0.0) or Fe"(0.25-0.0) Se'-(1.0-0.9)-Zn''(0.25-0.1) U'*(0.75-0.6)-Zr'-(0.0-0.0) VO^*(0.3-0.0)-Zn^-(0.6-0.45) or Cd'-(0.6-0.4)
1.0 M S F
M .0 M SF + 1.0 M FA (8:2)
1 . 0 M S F +
1.0 M FA (4; 6) 1.0 M S F + 1.0 M FA (6:4)
Tr(0.66-0.52)-Tp-(0.0-0.0) Cr^*(0.53-0.45)-Ni^-(1.0-0.9) Se'*(0.68-0.50)-Bi'l0.08-0.0) or Pb'-(O.O-O.O) Zn'*(0.83-0.7)-Ni^-(1.0-0.9) Cd^'(0.7-0.5)-Nl'*(1.0-0.8) Fe''(0.75-0.4)-Ni^* + Co"(1.0-0.8)
Reversed phase chromatography on SG impregnated with TBA gave excellent results. The thin layers were of good quality. However, the plates prepared by direct impregnation proved superior to those obtained by indirect impregnation. The time of development ranged from 1-2 h depending upon the mobile phase composition. The spots were compact and well formed in all solvent systems and at ail percent impregnations (10-70%) of TBA. However. Cd^*. Ag*, Hg2**, and Hg^* showed some tailing («L -RJ > 0.3) in some solvent systems. The R, values of metal ions were found to depend upon the time and temperature of drying of the impregnated SG plates. The plates were quite stable in acidic developers and also in 1.0 M SF but at a higher pH of mobile phase the plates were deformed on drying. Specifically, the plates developed in 5.0 M aqueous SF (pH - 7.75) were deformed
Journal of Planar Chromatography VOL. I.JUNE 1988 1 2 9
RP-TLC of Heavy Metal Ions
Table 2
Binary separations obtained on silica gel layers impregnated with 60% and 20% TBA using different solvent systems.
% Impreg- Solvent system Separations achieved (ft, - R,) nation with TBA
Table 4
Quarternary separations achieved on silica gel layers impregnated with 40% TBA by using solvent system containing 1.0 M SF and 1.0 M FA In an 8:2 ratio (ascent 12 cm).
Separations achieved (R^ - R,)
60 1.0 M FA
60 60
20
1.0 M S F
1.0MSF + 1.0 M FA (8:2)
1.0MSF + 1.0 M FA (8:2)
AP*(0.55-0.45)-Ni'*(0.8-0.7) Ti'*(0.0-0.0)-Np-(1-0-0.7) Ti'*(0.0-0.0)-Ta'*(0.95-0.45) Zn'*(0.0-0.0)-Ta'*(0.9-0.4) Zr^*(0.0-0.0)-Th**(0.8-0.45) Ti**(0.0-0.0)-Th'*(0.85-0.5) Mn^*(0.7-0.55)-BP'(D.D-0.0) VO^*(0.6-0.5)-T1^*(0.05-0.0) VO^*(0.6-0.5)-2r'*(0.05-0.0) VO^*(0.05-0.4)-W**(0.04-0.0) VCy *(0.45-0.3)-Cu'*(1.0-0.9) Vcy *(0.55-0.35)-Cu'*(1.0-0.9) Zn'*(0.1 -0.0)-Crf*(1.0-0.75) Zn'*(0.3-0.2)-Hg'*(0.04-0.0) Hg2*(0.35-0.25)-Ptf'(0.1-0.0) CU^*(0 .3-0 .2) -NP*(1 .0-0.9)
Cd='*(0.9-0.7)-Ag*(0.O-0.0) V(y*(0.2-0.0)-CkJ^*(0.9-0.7) VO^*(0.2-0.0)-Fe'*(0.63-0.45)
AI^*(0.2-0.17)-Cu^*(0.3-0.28)-NI^*(0.9-0.6)-Ti''-(0.0-0.0) AP* (0 .2 -0 . 15)-Cd='*(0.8-0.7)-Ni^*(0.9-0.8)-Ti*-(0.0-0.0)
Ti'*(0.0-0.0)-UO^*(0.46-0.44)-Co'*(1.0-0.9)-Ap-(0.15-0.14) Ti'*(0.0-0.0)-Zn^*(0.4-0.36)-Cd^*(0.9-0.75)-Ni^-(1.0-0.9) Ti**(0.0-0.0)-Co^*(1.0-0.8)-Cf^*(0.2-0.15)-Cd^*(0.63-0.52) Cr^'(0.07-0.0)-Bi^*(0.45-0.37)-Crf*(1.0-0.8)-Co^*(0.8-0.7) Cr'*(0.17-0.16)-Ag'(0.0-0.0)-Cd'*(0.85-0.73)
Table 5
TLC data for some metal ions on SG layers impregnated with 40% TBA using 1.0 M SF + 1.0 M FA (8:2) as solvent system.
Metal Ions/Metal salts
Cu^Vcopper chloride Ni^Vnickel sulfate Co^Vcobalt chloride Zn^Vzinc chloride Cd^Vcadmium nitrate
Concentration range loaded (pg)
1.0-400 0.5-400
10.0-600 0.5-400
10.0-200
Range of R, obtained
0.3 -0.37 0.94-1.0 0.9 -1.0 0.33-0.41 0.72-0.85
Lower detectability level (pg)
1.0 0.5
10.0 0.3 1.0
Table 3
Ternary separations achieved on silica gel layers impregnated with variable concentrations of TBA in different solvent systems.
% Impregnation with TBA Solvent system Separations achieved (ft^ - Ftr)
20
40
40
40
60 60
1.0MFA + 1 . 0 M S F ( 8 : 2 )
1.0 M FA + 1 . 0 M S F ( 8 : 2 )
1.0 M FA + 1 . 0 M S F ( 4 : 6 )
1.0 M FA + 1 . 0 M S F ( 6 : 4 )
1.0 M FA 1.0 M FA + 1 . 0 M S F ( 8 : 2 )
70 1.0 M S F +
1.0 M FA (8:2)
Zn'*(0.65-0.1)-Cd^*(0.9-0.7)-TI'*(0.0-0.0)
Ti**(0.0-0.0)-UO|*(0.36-0.33)-Ni^*(1.0-0.7) Ti**(0.0-0.0)-Zn'*(0.4-0.3)-Co'*(0.95-0.9) Ti**(0.0-0.0)-UOf(0.36-0.33)-NP*(1.0-0.87) Ti**(0.0-0.0)-UOf(0.36-0.33)-Co^*(1.0-0.85) VO^'(0.20-0.0)-UOr(0.48-0.4)-Ti'*(0.0-0.0) AP*(0.26-0.25)-Ti**(0.0-0.0)-Cd^'(0.55-0.5) AI'*(0.12-0.10)-Nl'*(1.0-0.9)-Ti**(0.0-0.0)
Co^*(0.85-0.7)-Ti**(0.0-0.0)-AP*(0.55-0.45) Cu'*(0.35-0.20)-Cd'*(1.0-0.8)-Pb^*(0.0-0.0) Zn='*(0.23-0.20)-Cd^*(0.95-0.8)-Pb'*(0.0-0.0) Zn'*(0.27-0.25)-Cd^*(0.95-0.8)-Hg|*(0.0-0.0) UO|*(0.27-0.25)-Fe"(0.1 -O.0)-Co='*(1.0-0.9) VO^*(0.1 -0.0)-Fe'*(0.35-0.3)-Co^*(1.0-0.9) Cu'*(0.3-0.2)-Ni^*(1.0-0.92)-Ag-(0.0-0.0) Cu'*(0.3-0.25)-Cd='*(0.97-0.8)-Bi^*(0.06-0.0) TP(0.23-0.2)-Cd^*(1.0-O.8)-Agl0.O-0.0) TI'*(0.23-0.2)-Hg='-(0.0-0.0)-Cd^*(1.0-0.8) TI'*(0.38-0.35)-Pb^*(0.1 -0.0)-Cd'*(1.0-0.95) TP*(0.27-0.25)-TI*(0.0-0.0)-Ni^-(1.0-0.95) Zn'*(0.22-0.15)-Cd^*(0.88-0.77)-Ti'-(0.0-0.0) Tt*(0.75-0.65)-Zn^-(0.3-0.18)-Bi'*(0.0-0.0) Zn^*(0.1 -0.05)-Tr(0.65-0.5)-Pb'-(0.0-0.0) UO|*(0.28-0.24)-Zr'*(0.0-0.0)-Co^-(0.95-0.8) Cu'*(0.3-0.25)-Co^*(1.0-0.9)-Ti*'(0.0-0.0) Cu^*(0.3-0.25)-Co^*(1.0-0.85)-Zr'*(0.0-0.0)
130 VOL. I.JUNE 1988 Journal ot Planar Ctirotnatography
RP-TLC of Heavy Metal Ions
Table 6
TLC parameters for the separation of Zn'* from Cd '
and Co'* with 1.0 M SF + 1.0 M FA (8:2) solvent system.
Ni '
% Impregnation with TBA
40
60
70
Separating cation pair
Zn-Cd Zn-Ni Zn-Co Zn-Cd Zn-Ni Zn-Co Zn-Cd Zn-Ni Zn-Co
TLC Afl,
0.52 0.52 0.48 0.65 0.71 0.69 0.73 0.78 0.72
Darameters a
10.1 16.3 11.98 25.69 60.76 45.14 48.8 86.6 39.6
Rs
5.3 4.38 5.3 4.66 7.00 7.00 5.33 9.62 6.27
on drying. The effects of various factors on the chromatographic behavior of metal ions are given below .
3.1 Effect of Aqueous SF Concentration on the Mobility of Metal Ions
On the basis of their chromatographic behavior on SG layers impregnated with 40% TBA in varying concentrations of SF (0.001 to 5.0 M), metal ions can be classified into the following groups:
(0 Metal ions such as U0|*, Fe^*, AP*, Ag*. Pb^*, B\^\ 1\^\ and Ti** showed no mobility over the entire range of SF concentrations. The low R, value for these metal ions may be attributed to the formation of anionic/neutral complexes with SF similar to those reported by Oureshi et a/. [27] for rew cations. HgJ* and Hg^* produced tailed spots starting from the point of application.
(iO Ni^* and Co^* moved with the solvent front giving high R, (= 0.9) over the whole concentration range. The absence of sorption in these cases may be attributed to the lack of formation of anionic metal formate complexes.
(iii) Metal ions like Tl* and Cd^* showed an increase in mobility with the increase in SF concentration giving fl, equal to 0.9 in 5 M SF. The increase in R, value with the increase in SF concentration is probably due to increased complexation at higher pH.
(Iv) Cu^* and Zn^* did not move in solvents containing up to 1.0 M SF. However, a sudden increase in their R, values was observed in 2.0 M and 5.0 M SF.
All the melal ions were detected satisfactorily at all SF concentrations (0.001-5.0 M). The development time increases with the ncrease in molar concentration of SF until it reaches to 2 h in 5.0 M SF.
3.2 Effect of FA Concentration on the Mobility of Metal Ions
The study of chromatographic behavior of metal ions on 40% TBA impregnated SG plates in acidic developers containing
varying molar concentrations of aqueous FA (0.001-20.0 M) gave some interesting results. The main points emerging from this study are as follows:
(i) HgJ'' formed elongated spots at all FA concentrations while Bi^* and Cd^* produced tailed spots (starting from the origin) in 5-20 M and 0.001 M - 0.1 M FA, respectively.
(ii) Ag*, Pb^*, and Ti"* remained at the point of application at all FA concentrations used. Conversely, Ni^* and Co^* moved with the solvent front, probably due to the solvation of these ions/complexes by the mobile phase.
(iii) UOl\ Fe^\ A!'*, Bi^\ Zn^\ Cr^*, Cu^\ and Cd^* did not move in mobile phases containing up to 0.1 M FA. On further increase in acid concentrations, these metal ions show significant mobility giving ft, 0.7-0.9 in 1.0 M FA. The R, values reach a maximum (R, = 1.0) at higher FA concentrations {i.e. 5-20 M). The higher FA concentration was found unsuitable because of (i) spreading of spots, C") longer development time (iii), less sharp detection of most of the metal ions.
The increase in W, with increasing molar concentration of FA is attributed to the increase in the number of H* ions competing with the cations or cationic complexes for the exchange sites.
3.3 Effect of TBA Impregnation on the Mobility of Metal Ions
Figure 1 shows that TBA impregnated SG layers are more strongly sorbing than unimpregnated or plain SG layers for
l.OMSF • l-OMSF + IOM FA (1:1)
+0.8
.•0-6
I •0-6 ARf
• 0-2
00
-0.2
catlons Figure 1
Comparison of s«lectjvjtles of TBA-impregnated and unimpregnated silica get layers in different solvent systems.
Journal o( Pla«Br Ciiromalogtnphv VOL I.JUNE 1988 1 3 1
RP-TLC of Heavy Metal Ions
most of the metal ions, as indicated by positive values of AWf. Here Afl( is the measure for the difference in the fl( values of metal ions on unimpregnated and impregnated SG layers, i.e. Afl, = fl, on unimpregnated SG layers - R, on impregnated SG layers. Thus, TBA impregnation enhances the selectivity of the plain SG layers.
Figure 2 shows the effect of the degree of impregnation of TBA on the R, values of metal ions in 1.0 M FA and in 1.0 M FA + 1.0 M SF (2:8) solvent systems. The R, values for only those cations which gave compact spots were taken for plotting the figures. It is evident from Figure 2 that, in 1.0 M FA, the R, values generally decrease with increasing degree of impregnation. However, Cd^* and Bi^* showed constancy of R, values at ail degrees of impregnation. Zn^* showed significant tailing (R, = 0.0-0.6) over 10-20% impregnation.
In solvent system containing a mixture of 1.0 M FA and 1.0 M SF in a ratio of 2:8, the plots (Figure 2) showed frequent fluctuations over the entire range of TBA impregnation. Interestingly, a few cations showed stronger sorption at 30% TBA impregnation. Detection of all metal ions was very clean and sharp at all degrees of impregnation but the spots were more compact at higher degrees. The shapes of these curves can be tentatively explained on the basis of the existence of a neutral, positive, or negative species as well as the possibie formation of less strongly adsorbed higher charged negative
complexes. Some other phenomena, such as the adsorption in the network of the support, precipitation in the network of the support, precipitation, hydrolysis, and solvent-solvent interactions, may play an important role affecting the sorption behavior of metal ions on impregnated SG layers.
3.4 Effect of Mixed Solvent Systems Containing Mixture of 1.0 M FA and 1.0 M SF on the Mobility of Metal Ions
It is clear from Figure 3a that 1.0 M SF is the best solvent for the separation of Zn^* from Cd^*, Ni^* and Co^* on 60% TBA impregnated SG layers. However, the separation of Cd^* from Zn^* in this solvent is also possible on 40% impregnated plates but the greater tailing of Cd^* decreases the resolution of its separation from Zn^* (Figure 3b). It is obvious from Figure 3b that 1.0 M SF behaves differently from 1.0 M FA as a mobile phase. Most of the cations move faster in FA and produce more compact spots compared to SF. Ni^* and Co^* show identical tjehavior in both the solvent systems and move with the solvent front. Figures 3c-d, summarize the chromatographic behavior of metal ions in solvent systems containing mixtures of 1.0 M FA and 1.0 M SF in different molar ratios. Evidently, most of the metal ions show relatively greater mobility and higher compactness in solvents containing tiigher percentages of FA.
_ j I 1 i _
r -o--
10 20 30 iO SO 60 70 V. impr«gr\Qtior\ w i t h T8A
10 20 JO 40 50 SO 70 ' / . . r r p r t g n o l i o n w i t h TBA
Rf 0
0
0
Rf 0
0
0.
s
c
4
2 -
0
-g,-- ' - g . - . ^ - . ^ : ^ ^
1 0
0 8
0-6
Rf 0 4
0 2
0 0
1*
- S - - 0 - - 0 -
" • - - o o — o I ^ t ^O-
~-c>-,o_ - 0 - - 0 - - < i > —
- - 0 - -
Tl
"^^^"^Q—^ --f—9 ^ -
Hg
10 20 30 4 0 50 60 70
V , imprtgnot ion wi th TBA 10 20 30 60 50 60 70
V . imprtgnotion with TBA
Figure 2
Plot of R, Vs percentage impregnation of TBA in t)€n7ene. - ® ® - 1.0 M FA; - i ' »•>- 1.0 M FA + 1.0 M SF (2:8) .
132 V O L 1, J U N E 1988 Journ.'^l of PInnnr Chfnrn.'i'' / j i .K'f ' .
RP-TLC of Heavy Metal Ions
1 OM SF
A-IOM SF»1 0MFA(«:2) B-IOM SF + 10MFA(2:8) C-)OM SF • )0M FA(1:))
A-VOMSF«).OH FA(S:4) B-lOM SF + 10MFA(4:6)
4 > O b . | Z o Z < - > N < u X X P p a . < 0 3 > -Utlons
Figures
Pkrt of R| n metal lone in different eoivent systems, a - 60% TBA impregnated SO layers. b ,cd • 40% TBA impregnated SG layers. • — • Compact spots; A — A TaBed spots virfth SL - n , > 0.4; O — O T a i M spots with R - RT < 0.4.
3.5 Effect of pH of Metal Solutions on the Separation ofZn^* from Ni**, Co**, and Cd**
Rgure 4 shows that the R, values of Zn^*, Ni^*, Co^\ and Cd * are independent of the pH of the sample solution in the pH range of 1-5. Thus a good separation of Zn^* from these metal ions can be obtained on 60% TBA impregnated SG
10
oe I 0 6(-
Rf0 4
0 2 •
00
Cd^ Ni *on4 Co?* - • m • •
2 3 t fH of fflttal tolution*
Figure 4
Plot of pH o< metal solutions M . R, on silica gel layers impregnated with 60% TBA In solvwil syslMn containtng l A i t SF and 1 . 0 M FA In an 8:2 ratio.
layers in mobile phase containing a mixture of 1,0 M SF and 1.0 M FA in 8:2 by using unbuffered sample solutions without adhering to the close control of the sample pH.
Enhancement of the selectivity of SG layers by impregnation with TBA provides an opportunity to achieve many analytically important separations. Many such separations have actually t>een realized and are tabulated in Tables 1-4. Separations such as Zn^*-Cd^\ AP*-CU^*, VCP*-TP*, VCP*-W*\
Th''*-Zr*\ Fe3*-TP^ AP^-Cu^^-Ni^^-Ti"*, Cr^^-BJ^*-Cd^^-Co^*, Zn^^-Cd^^-Pb^* and Zn^-'-Tr-Pb^* are worth mentioning.
Table 5 summarizes the results of the effect of loading on the fl( values and the lowest possible detectable amount of metal ions on the chromatoplates. TBA impregnated SG layers gave highly compact spots over a wide range of loading of the nrretal ions. 0.5 pg of Ni * gave R, equal to 0.94 while it is 1.0for400Mgof Ni *.
In order to present a clearer picture regarding the separation of Zn^* from Cd^*, Ni^*, and Co^*, someTLC parameters such as Afl, (ft, of separating metal ion - Rf of Zn^*), separation factor (a) and resolution (f?J have been calculated. These data are shown in Table 6. The values for a and Rg have t)een calculated by using the following relationships
(i) a
K' 1- f l ,
(M = separating metal)
where K' is a capacity factor which measures the degree of retention of a solute compared to the solvent.
fls M
1/2 (d, + dz)
where AX is the distance between the centers of spots and di, d2 are their respective diameters. Two solutes are just separated if R, is equal to 1. It is clear from Table 6 that a good separation of Zn^* from Gd^*, Ni *, and Go * can be carried out by the proposed method. The Afl| value is always greater than 0.5. A high value of separation factor and well resolved spots with H. > 5 are the added advantages of this study.
The proposed method, consisting in the use of 40-60% TBA impregnated SG layers and a mixture of 1.0 M SF and 1.0 M FA in a 8:2 ratio as developer is very reliable and reproduc-'Me for achieving the separation of a particular cation from others in general. It is especially useful if one needs sharper aix) clearer ternary and quartemary separations. The spots are so well formed and compact that good quartemary separations are always possible. It is a very reliable method for separating Zn^* from Cd^* over a reasonable pH range of sample solutions.
Journal cil Plan.ir Chromatopfaphy vol I .11 INF 19R8 133
RP-TLC of Heavy Metal Ions
Acknowledgment
The authors thank Prof A. U. Malik. Chairman, Department of Applied Chemistry, for providing facilities and the University Grants Commission (India) for financial assistance to N. Fatima.
References
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(3J E. Cerrai and 6. Ghersini. J. Chrcpatogr, 18 (1965) 124.
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Ms received: November 10, 1987 Accepted by SN: January 5, 1988
134 VOL. I.JUNE 1988 Journal of Planar Chromatograptiy