Lec 05
Lec 05
Professor V. C. Srivastava
Department of Chemical Engineering
Indian Institute of Technology Roorkee
Lecture 5
Water Quality Monitoring Chemical Parameters - I
Good day everyone, and welcome to this lecture on water quality monitoring in the course on
Physico-chemical processes for wastewater treatment. So, in the previous lecture actually we
discussed regarding chemical parameters, and in the last we were discussing regarding the
various ions which are present in the water. So, we will be broadly continuing with the same
topic and interpret various chemical parameters if there are various ions present in the water.
So, we will be continuing with the chemical parameters, and within the ions after determining
the various ions which are present in the water, we can interpret various results with respect
to various parameters, and one of the important parameters is hardness.
So, presence of hardness in the water causes many problems, and these problems may be the
lathering of the soap during the cleaning of the clothes in the households. So, if hardness is
there, so, the cleaning of clothes becomes very difficult because the whichever soap we are
using, that gets lathered away and that is actually not used in the cleaning itself.
And then also in the industries, industries require water we should have minimum hardness, if
that water has to be used for a steam generation and also as a utility, because if the water has
to be heated, if any of the hardness and other types of ions are present in the water, then that
forms scales which is not desirable.
So, why this hardness is present, how to measure this hardness and what are its classifications
that we are going to learn. So, this hardness is due to the presence of calcium and magnesium
ions in its various forms. So, that may be the carbonate form or sulphate form of calcium and
magnesium ions. And these are due to the presence of also these calcium and magnesium ions
may be due to their chloride form or nitrate form, but generally carbonate form and sulphate
form are more present.
Now, hardness, why hardness causes soap scum that is there because the Ca 2 plus is like
which is the major ion in the hardness it interacts with soap anions and forms a neutral specie
which is like calcium combining with the soap. So, that actually, whichever soap we are
using, its anionic form easily combined with the calcium, in place of combining with the dirt
and other things. So, this causes the scum.
Similarly, scaling of the pipes, which occurs because of the presence of calcium and
magnesium ions in the water, is due to the conversion of bicarbonate form of these calcium
and magnesium ions in to calcium carbonate and magnesium carbonate forms which are
basically a solid state species and they get settle on this pipe forming the scales and these
calcium carbonate and magnesium carbonate they cause various problems because they will
be in crystalline form and slowly and slowly they will accumulate.
So, the corrosion and other issues start happening within the pipes. So, they cause lot of
problems. Similarly, if the water is to be used in the steam turbine or other places for
generation of steam, and that steam has to be further used. So, which whichever place that
water is there, which contains this hardness, it will have lots of issues, also these hardness
things they leave lot of stains on the plumbing fixtures whichever may be there in the whole
pipeline system. So, they have lot of issues there. So, how we determine the hardness?
For determining the hardness in water, the general very common method which is there, that
water is titrated against EDTA salt solution using Eriochrome Black T as indicator, and this
method is called Versenate method and this is very common method, and during the titration
actually the colour changes from wine red to blue.
And there are certain classification of water based upon hardness, if the water is having
hardness less than 75 milligram per liter then that water is called as soft, whereas, if the water
is having hardness more than 200 milligram per liter, there, these water are considered as
hard water, and in between they are moderately hard.
So, this is their underground water generally is harder than the surface water, because, they
have more chances of accumulating calcium and magnesium from the various rocks and also
because the carbonate, bicarbonate and carbonate ions always occur in the water due to the
natural dissolution of CO2 into water.
So, they form these calcium carbonate, calcium bicarbonate and other things and their present
is more in the groundwater as compared to in the surface water. For boiler-feed water or for
efficient cloth washing the water must be soft. So, this is desirable. So, the hardness should
be at least less than 75 milligram per liter. For drinking purpose if hardness is higher also
there is no issue it causes no problem as such.
Now, how hardness gets formed or gets into the water. So, during normal condition in the
soil, we have topsoil, subsoil and limestone at the bottom. Now, whenever there is rain or
precipitation that happens, likely it will percolate through this topsoil.
And in the subsoil if CO2 is there, which may have also percolated during the period when
the rain was not there. So, this CO2 will combine with H2O. So, we can have lot of
bicarbonate which will be there, and these bicarbonates later on combine with calcium
carbonate and magnesium carbonate rocks, which may be present like in the limestone and
they combine with them to form the calcium bicarbonate and magnesium bicarbonate, and
these get dissolved into the water.
So, that is why the groundwater has more hardness as compared to the surface water and this
is how the hardness comes into the water. Now, types of hardness there are like we have
already defined the total hardness is like addition of calcium and magnesium and present in
the water.
(Refer Slide Time: 7:47)
So, the hardness can also be defined in terms of carbonate hardness or non-carbonate
hardness. So, if hardness is associated with bicarbonate ion, or carbonate and it is called as
carbonate hardness. If it is associated with other anions then it is called as non-carbonate
hardness. So, here some values and example is given in this figure. So, we can see the
calcium and magnesium is present up to 6.99 milliequivalents per liter.
Now, out of this the carbonate, bicarbonate ion is present, no carbonate ion is present, and
after we have sulphate and chloride ion. Now, whatever hardness which is associated with
carbonate or bicarbonate ion, it is called as carbonate hardness. So, we have up till 2.74
milliequivalents per liter, it is called as carbonate hardness, and beyond that whatever is the
value that is the non-carbonate hardness which can be obtained by subtracting the carbonate
hardness from the total hardness value.
So, this is there. Now, out of the other hardness we can define in terms of calcium hardness
and magnesium hardness also. So, calcium hardness is generally considered first. So, calcium
in the present case whole of the calcium hardness is because of two reasons, one is carbonate
hardness and another is non carbonate hardness.
So, one fraction is from here, and then second fraction of calcium hardness which is
associated with non-carbonate hardness. And then whole of the magnesium hardness is
associated with the non-carbonate hardness, which is given here. So, we can interpret many
results out of these type of diagrams. So, we will continue to learn.
(Refer Slide Time: 9:47)
Now, after this calcium and magnesium, which is which are associated with the hardness
there is another very important element which is called as sodium. Generally, people neglect
this sodium ions, but sodium ions have lot of importance with respect to irrigation of water,
also their essential salts which must be there in the water for our uses.
So, we have a dilemma here at how much sodium should be present, and sodium is always
present in the water because it is one of the most abundant element on the planet. Now, high
concentration of sodium in inland waters, it is associated with discharges from either
industry, or sewage effluent, which is coming out of the residential colonies and other places.
So, this is there. So, if any water contains high amount of sodium, it may be because of this.
Also in the coastal areas, sea water intrusion may occur. So, the lakes and reservoirs which
are close to coastal areas may have higher amount of sodium as compared to inland water,
lakes or other reservoirs. So, normally sodium concentrations should be below two hundred
milligram per liter.
So, this is the usual case, sodium as such is nontoxic though it has a bitter taste. Now, health
hazards which are there because of sodium, we know very well that there is there are issues
that blood pressure may be high if we have more sodium in our blood, and also cardiac and
kidney issues may happen if the sodium concentration in the water is high, and we are
continuously taking water with higher sodium concentration.
Now standard for sodium is that it should be below two hundred fifty milligram per liter.
Now, there are many parameters which are directly related to sodium. So, one by one, we will
try to understand those parameters, and they are related to irrigation and other things.
So, which water has to be used for irrigation or otherwise, some of the examples are given in
today's lecture, but there are many other parameters also, which will not be covered because
they will require a very detailed lecture, or a separate course may be itself. So, sodium has a
negative effect on the soil structure.
Because it deflocculates the soil, and we have seen that in all those soils which have, which
are not fertile, they have some fluffy type of things. So, they contain lot of sodium and
because of deflocculating nature, it becomes fluffy or otherwise. So, it actually has a negative
effect and the fertility of that soil is very, very less.
To evaluate the suitability of any water for irrigation, there is one term which is called as
sodium absorption ratio and that is used. So, there are parameters, how it is defined in the
short form we call it SAR. So, SAR is like ratio of Na+ divided by the average under root of
average of calcium and magnesium ions. So, this is how it is defined, and all the
concentrations in this equations have to be used in milliequivalents per liter.
To evaluate the suitability of water for irrigation, the Sodium Adsorption Ration (SAR) is
used as follows:
Na +
SAR =
(Ca + + Mg 2+ ) / 2
where, the concentration of the ions in meq/L are used.
Now, if SAR value is less than three, the water is suitable for irrigation use. So, it is good that
if you can have a irrigation water which is having SAR value of less than three. Now,
between three and nine, we can still use the water with some restriction, but if SAR value is
more than nine, that means that water is not good enough for us as irrigation and in the long
run, if we continuously use that water, then there may be issues and the whole of the land
may become infertile also.
So, this is a possibility, in India however at many places that irrigation water with very large
SAR values are being used. So, this is a, this will cause lot of problems in long run. So, they,
we should understand these things and determine the SAR values after, for all the waters that
we are using for irrigation and we should find out the SAR values for all the canal systems
which are there, which are being used further for irrigation.
(Refer Slide Time: 14:46)
Now, there is another parameter which is related to sodium, it is called sodium percentage.
So, this is basically how much percentage of sodium is there vis-a-vis sodium, calcium,
potassium and magnesium, and all values are expressed in milliequivalents per liter. So, this
is the formula which is given here. So, this is, it is recommended, certainly that sodium
percentage should not be, should not exceed sixty percent.
So, the majority of the total cations which are there, the sodium value should be restricted
less than sixty. So, this is there, in waters where bicarbonate content is high. So, that means
water which are having more amount of bicarbonate, there is a tendency for calcium and
magnesium which present to precipitate out. And if they are getting precipitated out, we have
higher percentage of SAR as well as the sodium percentage.
So, it has a problem. So, another parameter was defined, which is called as residual sodium
carbonate. And it is like difference between the carbonate ion, bicarbonate ion, and the
calcium and magnesium ion. So, this RSC was defined in short form we call it RSC and if its
value exceeds two point five milliequivalents per liter, the water is not suitable for irrigation,
between 2.5 to 1.25. It is a marginal value it can be used and less than 1.25 it is considered to
be safe. So, we have three parameters which are related to sodium.
(Refer Slide Time: 16:33)
Now, what we do is that we will solve one problem with respect to in a water the
concentration of cations and anions are given, and we have to find out different parameters
out of this. So, we have all the cations which are reported here, and the anions, and their
concentration in water is reported.
Now, what we have to do is that, we have to find out that TDS, total hardness, carbonate or
which is called as temporary hardness, that also we have to find out, then we have to find out
non-carbonate or permanent hardness, then sodium absorption ratio SAR value, percentage
sodium, and the RSC in milliequivalents per liter. So, these parameters we can get from this
table itself. So, we will try to solve it.
So, we have converted all the milliequivalent per liter, for both all the cations as well as all
the anions. It may be noted here that in this example, it is given that the carbonate is zero in
the water, but these are arbitrary values we which we have taken here just for demonstrating
that how we can perform the calculations in the actual case the carbonate value may be
present may not be present.
Now, what we do is that, if we have to find out the first we should always cross check that
what is the error in the sum of cations and sum of anions, so and what is the error so, that
through that we can check whether the results which have been reported in this analysis
report are correct or not. So, all this anions are added together, and all the cations and anions
both are added together.
Now, out of that we can calculate the carbonate hardness or temporary hardness, which is
associated with carbonate. So, for doing this we can easily see because the value of calcium
and magnesium is much higher than the carbonate. So, value which is 2.377. So, that means
the carbonate hardness is 2.377, and now rest of the hardness we can find out by subtracting.
So, this is 3.873, and both if we add them together the value should be 6.250.
So, this is there. TDS is like adding the all the concentrations of cations and anions they have
been just added here and this is the value. So, this is straight forward. SAR value as per the
formula, because the milliequivalent is given. So, we can calculate so, it was found to be
1.230 so, this 1.230 is less than three, so, that means, this water is suitable for irrigation.
So, this is this is the inference that we can obtain similarly, percentage sodium is also less
than 60 percent. So, that is that also tells that we have good water which can be used for
irrigation, by chance for this this particular analysis the RSC value is negative and it is not
always possible to have the all the results in our positive value.
So, it will depend on various things. So, this is okay, we can either neglect it or otherwise, but
these two parameters tell us that water is good enough for irrigation. So, by finding out only
all the major anions and cations we are able to find out so many parameters out of this, and it
helps in determining whether our water is good enough for drinking of for irrigation or not.
Now continuing, there are other parameters which are very important and one of the
parameters is like potassium. So, it is always present in low quantity in natural freshwater.
So, generally it should be less than, it will be less than 10 milligram per liter. Seawater and
brines they contain much higher concentration, a potassium ions are highly soluble, and they
are essential forms of life. So, as such, they are not that much toxic or anything they no issue
with respect to potassium, but there is an issue that if they are present in water and that water
from after the it is being discharged to some of the lakes and reservoirs.
So, under those conditions, if we have to stop the aquatic life to grow maybe plants, so we
have to see that the potassium value should be under certain limit. So, as such it is not a very
important parameter, sometimes it is taken care of, so that we can get enough potassium from
the water itself to our body. So, this is there. Then another parameter which is called as
sulphate.
The sulphate is present in all surface waters. And it is because it is it comes sulphate comes
from various rocks and from seawater also. So, seawater generally contain very high sulphate
concentration, and rocks also give a lot of sulphate into the water. So, the groundwater may
contain sulphate also. High concentration of sulphate in any water makes the water highly
corrosive to the building material, in particular the concrete.
So, this is the very deterrent thing with respect to sulphate, then it may also be causing the
scale formation. So, that is another bad thing with respect to sulphate. And it is capable of
being reduced to hydrogen sulphide. So, if sulphate gets reduced to hydrogen sulphide, so it
will emit a foul smell. So, we can easily see that okay, H2S formation is taking place, and this
may happen in underground water also, where the zero dissolved oxygen conditions are
prevailing. So, we do not want this condition to be raise. Generally, H2S is very undesirable.
So, there is a particular limit with respect to sulphate concentration in surface water, it should
be between 2 and 80 milligram per liter, but many places up to thousand milligram per liter
also have been reported, if the water is from industrial discharges also. Indian standard with
respect to sulphate is 200 milligram per liter.
(Refer Slide Time: 24:43)
Then similarly, we have chloride ions which are there, the sodium chloride is the main
substance in chloride. So, if sodium is present more likelihood that chloride will also be
present. So, natural water which is near the mines, or sea has lot of dissolved sodium
chloride. So, that means chloride will be present in the water, and excess of chloride is
considered to be dangerous, and it makes the water unfit for many uses.
And chloride concentration can be determined by titration method using silver nitrate and
potassium chromate, and this is very commonly used method for determining the chloride,
and in this method actually, the appearance of reddish colour confirms the presence of
chloride in the water. And there is a standard calibration method through which we can
determine the chloride concentration via this titration method. Chloride in the freshwater also
comes from the rocks.
(Refer Slide Time: 25:50)
So, there is a possibility of if other rocks in particular chloride rocks are there. So, they may
lease some of the chloride and that may go into the water. Fresh water concentrations of
chloride are normally less than 40 milligram per liter, and generally they can be as low as two
milligram per liters also.
So, drinking water is standard with respect to chloride is 250 milligrams per liter, and if any
water is having any salty taste, so, that means, it may be having chloride concentration more
than 100 milligram per liter, but up to 250 milligram per liter, it is okay to use the water for
drinking purpose.
So, corrosion is, corrosion of the various equipments and other things where water has to be
used. And in particular in pipe, that may be because of the presence of iron and manganese.
And they also cause a lot of taste and odor in the water. So, again colorimetric methods are
used for determining the quantity of iron and manganese in the water. So, there are various
methods which are present, and iron and manganese actually gets dissolved from the rock.
So, this is shown in this particular slide, and that happens because of the weathering effect
which is due to the CO2 which is going into the underground, and that causes the weathering
of these rocks and from which the iron goes into the water. Iran exist in various minerals as
such as ferrous sulphide, manganese also exists in manganese dioxide.
Generally, they are insoluble but in presence of CO2, they will leach out and go into the
water. And there are various soluble, various wells and anaerobic reservoirs where oxygen is
very less they will be soluble and they will be invisible that means, they will not impart
colour. So, we may feel that they are not containing iron and other things, but they may
contain. The Indian standards have been set with respect to iron as point three milligram per
liter and minus point zero five milligram per liter.
The pH of water which is there, earlier in the previous lecture, we discussed the pH. So, pH
has very important role, how much amount of iron or manganese will dissolve into the water.
So, generally natural water has a pH in the range of six and eight, but it may vary for
industrial wastewater. So, they may contain more amount of these iron and manganese. So,
they may have issues also with this.
Similarly, nitrogen is a element which can exist in the water in different forms. So, nitrogen
has a large number of valences, and managing nitrogen in the water cycle is one of the key
aspects in the present era in terms of research also and otherwise as well. So, in the form of
nitrogen may be in the form of nitrites, nitrates, free ammonia, and albuminoidal nitrogen etc.
And this this presence of nitrogen in the water indicates that there is lot of organic matter
present in the water.
Now, nitrogen is present in the water and that water is going into any aquatic body. So, we
have challenges that eutrophication may happen. So, this is possible. So, we always limit the
nitrogen. So, removing the nutrients in particular the nitrogen out of the water is very
important, if nitrogen is present in the nitrite form due to the partially oxidized organic
matter, then it is very dangerous.
Nitrite has more toxicity and in no case nitrite should be allowed in the water. Nitrites are
easily converted into nitrates, if we can fully oxidised the all the organic matter. So, it is
possible.
(Refer Slide Time: 30:41)
Now, nitrates are not that much harmful as nitrites but still there are certain reports which
told that nitrate is present in more than forty-five milligram per litre, they can cause disease
like methemoglobinemia disease to the children. So, this one of the disease which is reported
in the various places. Free ammonia is obtained from the decomposition of the organic matter
in the beginning. So, this is another form of nitrogen, free ammonia.
And if free ammonia is present in the water it will indicate that organic matters are
decomposition, their decomposition has started and generally the formation of free ammonia
will take lot of time. But still, it indicates the decomposition of all the nitrogenous organic
matter in the presence of, in the present in the water.
The presence of nitrites indicates partial decomposition of organic matters, whereas the
presence of nitrates indicates full oxidised matters. In summary, nitrogen is one of the
undesirable element, we do not want nitrites to be present at all. This is one important aspect,
second thing if nitrite is present can we convert in to nitrate, this is possible.
And, we should also after converting into nitrate also we should limit the nitrate within forty-
five milligram per litre, which is the standard, which causes diseases to the children, so this is
the important consideration. While treatment, when the treatment of wastewater or water has
to be done which contains nitrogen.
(Refer Slide Time: 32:33)
So, these are the some of the references for today’s lecture, and will continue the chemical
parameter in the next lecture. So, and there are many other chemical parameter of
importance, so that we will study in the next lecture.