WATER CHEMISTRY GUIDELINES FOR HIGH PRESSURE BOILERS

PUB.NO. 2003

CONTENTS
1.0 GENERAL 1.1 MAKE - UP WATER TREATMENT 1.2 1.3 1.4 INTERNAL CORROSION EFFECT OF pH EFFECT OF OXYGEN

1.5 BOILER W ATER TREATMENT 1.6 CONDENSER LEAKAGE FIG.1 FIG.2 FIG. 3 FIG. 4 FIG. 5 FIG. 6 FIG. 7 RELATIVE CORROSION RATE OF CARBON STEEL VS pH SILICA VS DRUM PRESSURE SILICA IN BOILER WATER VS DRUM PRESSURE OPERATION BETWEEN 70 - 125 kg/cm2 OPERATION BETWEEN 126 - 165 kg/cm2 OPERATION BETWEEN 166 - 182 kg/cm2 OPERATION BETWEEN 183 - 203 kg/cm2

RECOMMENDED FEED WATER LIMITS BOILER WATER LIMITS GUIDELINES FOR EMERGENCY OPERATIONS HOT WELL CONDITIONS FOR ALL VOLATILE TREATMENT

WATER TREATMENT
1.0 GENERAL High pressure boiler (operating above 60 kg/cm2 ) design needs a close look at the limiting conditions like heat transfer, heat exchanger metal temperature,circulation etc., The entire exercise of Water Treatment (both internal and external treatments) is aimed at (1) corrosion control and (2) steam quality. The cost of corrosion and deposition to electric utilities is very high due to repairs and loss of production (shutdowns).Poor steam quality leads to deposition on turbine blades causing efficiency loss and failures .Thus the successful operation of high pressure boilers and turbine units require a strict vigil on the Water Treatment practices and controls, particularly for high pressure drum type and once through boilers. 1.1 MAKE - UP WATER TREATMENT Trouble free continuous operations of high pressure boilers call for very stringent feed water quality. Total solids and silica, other than corrosion products,being the main constituents are responsible for carry-over and deposition reducing the units efficiency. Make up water is required to becontrolled and maintained at low levels. Silica in particular, is CARRIEDOVER in the form of VAPOUR at high pressures, needs to be controlled at low levels.Feed water is used for de-superheating spray and any contamination of feed water (either from steam condensate or from make up water) directly enters the superheated steam . IMPURE FEED WATER increases BLOW DOWN making the operation un-economical.Hence feed water is required to be very pure for high pressure boilers. This inturn necessitates high purity make up water, other than polishing the steam condensate, wherever applicable. Modern demineralisation plants with different combinations of ion-exchangers, are capable of producing the required quality of make up water with specific electrical conductivity less than 0.2 micro mhos/cm and silica 0.02/0.01 ppm. 1.2 INTERNAL CORROSION Corrosion is a common phenomenon in high pressure boilers. Corrosion in boiler circuits as well as in pre-boiler circuits can cause tube failures followed by force shut down of boilers.

The causes of corrosion are, i. ii. iii. iv. v. vi.

pH ( acidity or high alkalinity )

Oxygen Excessive ammonia (on copper base alloys ) Concentration of alkalising agents due to localised over heating Poor quality of passivating layer or breaking of passivating layer due to thermal shocks Decomposition of organics into corrosive products.

1.3

EFFECT OF pH The reaction of feed water on steel is spontaneous and rapid at high temperatures. The only reason that boiler steel can survive normal operating conditions is that the passivated layer of magnetite ( Fe3 O4 ) / hydrated iron oxide (FeOOH) forms a protective layer on the steel surface, preventing corrosion. The whole exercise of maintaining alkalinity control is to maintain an environment in which the oxide film is stable and protective. One of the objectives of Water Treatment in boilers is to protect this film against the aggressive action of impurities introduced into the boiler with the feed water. The work of Bell and Van Track has been used to relate the relative corrosion of steel over a range of pH values. It was found that the protective layer is getting dissolved at pH values below 5.0 and above 13.0 Minimum corrosion is indicated at pH of 9.0 to 11.0 (Fig. 1) Although corrosion is low over a wide band of pH values, unfortunately, corrosion occurs by localised concentration of alkaline chemicals on tube metal due to starvation, localised over heating etc. Rather than the concentrations existing in the bulk boiler water. Local concentration changes the pH drastically and corrosion takes place. Due to limitations of chemicals used, an optimum pH of 8.8 to 9.2 is recommended for feed water, which can be achieved by use of not more than 0.5 pprn of ammonia. Any excess presence of ammonia (indicated by higher pH values) will cause copper corrosion in the pre-boiler system. Another parameter which affects corrosion rate is the temperature inside the reaction vessel. Hence different temperature ranges or the pressure ranges call for different pH values to be maintained in order to minimize corrosion. Accordingly boiler water pH requirements are higher than the feed water limits and different for different pressure ranges. Boiler water pH is elevated to the recommended levels using Trisodium phosphate. The use of caustic soda is not recommended for this purpose as it has the danger of concentration and destruction of protective oxide film to cause corrosion.

1.4

EFFECT OF OXYGEN The exclusion of oxygen in feed water is essential to avoid corrosion. Small quantities of dissolved oxygen are capable of causing severe corrosion pitting in boiler tubes. A combination of poor oxygen control and chlorides in boiler water can result in serious hydrogen damage type corrosion of water wall tubes. Power plants employee tight cycles to prevent oxygen infiltration and condenser leakage are generally free from corrosion problems. Continuous monitoring of oxygen is required in high pressure system. Too often, oxygen enters the system undetected during periods of operation which are poorly monitored. Poor start-up procedures are also responsible for oxygen ingress. A most common error is the use of undeaerated water. Feed water at a temperature less than 100 deg. C contains excessive quantities of dissolved oxygen and hence feed water should never be allowed into the boiler at any time below this temperature.Deaerator is the main equipment to control oxygen within 0.01 - 0.02 ppm.

The best deaeration is obtained in units which operate above atmospheric pressure at all load conditions. A normal contamination of feed water occurs, when the deaerator pressure varies with a turbine bleed stage from above atmospheric to vacuum at low loads. Heater drips from low pressure system contain varied quantities of oxygen. A significant oxygen increase occurs in the heater drips as a heater drops below atmospheric pressure at low loads. A major problem of oxygen leakage occurs at low loads when heater drips are pumped directly to the condensate system. It is preferable to exhaust the drains to the deaerating section of the condenser. The most serious corrosion occurs in boilers which shut-down and start-up frequently without incorporation of technique to minimise oxygen in the feed water. Much of the problems can be reduced by pressurising the deaerator with steam at about 0.5 kg/cm2 (g) to exclude oxygen from the water during any short outage. For long outages, the vapour and water contacted surfaces of the feed water system should be pressurised with steam or nitrogen. With the main oxygen removal by deaeration, residual oxygen in small quantities can be reduced further by reducing agents such as sodium sulphite or hydrazine.Hydrazine being a volatile chemical, should only be used for high pressure boilers. Hydrazine reacts with oxygen to form nitrogen and water. This reaction is very low at temperatures below 175o C. Above 230o C, Hydrazine is decomposed rapidly to nitrogen, hydrogen and ammonia. Hence hydrazine dozing alone cannot control oxygen without effective deaeration. Since hydrazine has also the property of passivating the metal surfaces of the pre-boiler cycle by reducing the oxidised form of iron and copper, it is advantageous to add hydrazine to the cycle at the outlet of the condensate pump. 1.5 BOILER WATER TREATMENT It is recommended to use co-ordinated phosphate - pH treatment ( Sodium to phosphate ratio = 3) method for high treatment excludes free caustic from the boiler water. Caustic present in boiler results in a ductile-gouging type corrosion. Even if bulk boiler water does not contain large amount of free caustic, there is great potential for caustic to concentrate and cause corrosion. Internal metal oxide deposits provide sites for concentration. As steam is produced, dissolved solids concentrate in the thin film between tube wall and bulk fluid. Low sloped tubes permit concentration. It has been well established that phosphate even concentrated under hide-out conditions is not aggressive to the tube metal. Congruent phosphate program (Sodium to phosphate ratio = 2.6) takes care of both caustic and acid corrosion but control of sodium to phosphate ratio is difficult, calling for continuous feed and blow down. Figs. 4 to 7 provide guidelines to use either of the programmes, subject to the operators convenience. Volatile treatment is another method of treatment but it is primarily to control corrosion of heater surfaces in the pre - boiler circuit. Chemicals such as ammonia, cyclohexylamine and morpholine are volatile at high pressure boiler water temperatures. As a result there is no significant buffering of boiler water pH due to these chemicals. Any ingress of condenser leakage contaminants requires the immediate addition of phosphate to prevent the depression of pH and the incidence of hydrogen damage. The main attraction of volatile treatment is that it assures good steam purity . 5

Impurities due to vaporization of salts and mechanical carry-over are at a minimum.But it is necessary to employ condensate polishing and have reliable instrumentation for detecting immediately any condenser leak to safety operate with volatile treatment. 1.6 CONDENSER LEAKAGE Condenser leakage, as mentioned earlier, is a major source for corrosion. The type of cooling water and its interaction with boiler water determines whether b oiler water pH will become more acidic or alkaline during a period of condenser leakage. It is very important to prevent condenser leakage of sea water as it results in acidic boiler water. The hardness chloride salts present abundantly in sea water generate hydrochloric acids at boiler water temperatures. Uncontrolled large leakages of sea water can cause within hours extensive corrosion (hydrogen damage) of water wall tubes. There should be no hesitation to shutdown and save the unit if boiler water specifications,as recommended cannot be maintained during the condenser leakage. Any unit should have an on-line instrument with a cation column at the outlet of condenser to monitor conductivity continuously and detect immediately any condenser leakage.

FIG.1 RELATIVE CORROSION RATE OF CARBON STEEL VS pH

FIG.2 SILICA VS DRUM PRESSURE

6

FIG. 3 SILICA IN BOILER WATER VS DRUM PRESSURE

FIG. 4 OPERATION BETWEEN 70 - 125 kg/cm2

FIG. 5 OPERATION BETWEEN 126 - 165 kg/cm2

FIG. 6 OPERATION BETWEEN 166 - 182 kg/cm2

FIG. 7 OPERATION BETWEEN 183 - 203 kg/cm2

RECOMMENDED FEED WATER LIMITS

ONCE THROUGH BOILERS

DRUM OPERATING PRESSURE Kg/cm2 (g)

61-100

100 and above

TREATMENT TYPE 1. Hardness ppm (max) 2. pH at 250C 3. Sp. electrical conductivity after cation in H+ form at 250 C micro mho s/cm (max) 4. Dissolved oxygen ppb (max) 5. Silica as SiO 2 ppb (max) 6. Iron as Fe ppb (max) 7. Copper as Cu ppb (max) 8. Residual Hydrazene ppb

P04 NIL

P04 NIL

AVT NIL

AVT NIL

8.8-9.2 8.8-9.2 8.8-9.2 8.8-9.2 0.50 0.30 0.20 0.20

5.0 20.0 10 10 10-20.

5.0

5.0

5.0 10 10 3 10-20

20/10* 10 5 5/3* 10-20 10 3 10-20

* Should match with the corresponding values to be maintained in super heated steam
9

BOILER WATER LIMITS

(FOR DRUM TYPE BOILERS NORMAL OPERATION)

DRUM OPERATING PRESSURES Kg/cm 2 (g) TREATMENT TYPE 1. Total Dissolved solids ppm (max ) 2. Sp. Electrical conductivity micro. mhos/ cm (max) 3. Silica as Sio 2 ppm (max) 4. Chlorides 5. pH at 25o C ppm (max)

61 90

91 125

125 165

165 180

181 & above

PO4 100 200 4.0 9.0-10.0 5 20

PO4 100 200

To be controlled as per fig.2&3 9.0-10.0 5 20

PO4 50 100 0.20 9.1-9.8 5 20

PO4

AVT

PO4

AVT

15 2.0 (Note) 30 4.0 (Note) 0.10 0.10 0.6 9.1-9.7 26 0.02 9.3-9.5 N/A

10 1.0 (Note) 20 2.0 0.10 0.50 9.1-9.7 26 0.10 0.01 9.3-9.5 N/A

6. Phosphate, residual

ppm

* NOTE : Total solids 15 & 10 ppm correspond to 10 ppb sodium steam

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GUIDELINES FOR EMERGENCY OPERATIONS (DRUM TYPE - PHOSPHATE TREATMENT)

SI.NoPressure Hot well solids Operational ppm Limitations . range kg/sq c.m (g)
01 6 1 -1 2 5 0 . 5 -.2.0 (ABNORMAL) Limited operation Note.1 Emergency operation Note.3 Limited operation Note. I Emergency operation Note.3 Limited operation Note. 1 Emergency operation Note.3 Limited Operation Note 1 Emergency operation Note.3

Control Limits

Boiler Water Control

NOTE 2

TDS< 200 pprn p H 9 . 1 - 10.1 P 0 4 5 -4 0 p p m

> 2.0 (EXCESSIVE) 02. 1 2 6 -1 6 5 0 . 5 -2 . 0 (ABNORMAL)

NOTE 4 -D O TDS<100ppm p H 9 . 1 - 10.1 P 0 4 5 -2 0 p p r n NOTE2

03.

1 6 6 -1 8 0

> 2.0 (EXCESSIVE) 0 . 2 5 -1 . 0 (ABNORMAL)

-D O TDS<50ppm p H 9 . 1 - 10.1 P 0 4 5 -2 0 0 ' p r n

NOTE4 NOTE2

> 1 .0 (EXCESSiVE) 04. 1 8 1 -2 0 3 0 . 1 -1 . 0 (ABNORMAL)

-D O TDS<50ppm pH 9 . 1 - 10.1 P 0 4 5 -2 0 PPM

NOTE4 NOTE2

> 1.0 (EXCESSIVE)

NOTE4 -D O -

NOTE 1: Schedule Inspection and repair of condenser as soon as possible

NOTE 2: Immediately start chemical injection to achieve higher phosphate and pH condition not continue operation if pH cannot be maintained above 8 total solids below specified limits. Avoid use of desuper heating spray. NOTE 3: Immediately reduce load to permit isolation of damaged condenser and prepare for orderly shutdown if hot well TDS cannot be re duced quickly below specified limits. NOTE 4: Prepare for wet lay up of the boiler NOTE 5: Control silica in boiler water in accordance with graph provided.

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HOT WELL CONDITIONS FOR ALL VOLATILE TREATMENT

(FOR DRUM TYPE BOILERS)

PRESSURE RANGE (Kg/sq.cm)

HOT WELL SOLIDS (PPM) NORMAL OPERATION EMERGENCY OPERATION

126-165 Above 166 Note:

< 0.05 < 0.05

< 0.1 PPM < 0.25 PPM

Switch over to phosphate treatment when hot well solids exceed emergency operation levels.

GENERAL INSTRUCTIONS 1 . All Feed water measurements shall be made at high pressure heater outlet or economiser inlet . 2. Oxygen can also be additinrially measured at deaerator outlet to determine the quantity of N2 H4 dozing . 3. The recommended pH in feed water can be obtained by dozing ammonia, morpholine or any volatile amine. The concentration of volatile chemical in the feed water should not exceed 0.5 ppm.(expressed as Ammonia) 4. The phosphate and pH are recommended in accordance with co-ordinated phosphate curves (Figs. 4 to 7) to prevent presence of free hydroxide in boiler water. 5. Water levels in drum should be maintained within limits during all operational modes, start-up, load fluctuation and normal operation. 6. The allignment of drum internals should be checked and ensured to be in order atleast once every year 7. It is needless to emphasize that correct sampling, accurate measurements with the use of reliable instruments at adequate intervals and proper logging of readings go a long way in ensuring trouble free operation.

12

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METHODS OF WATER ANALYSIS

PUB.NO. 2019

CONTENTS
1. GENERAL INSTRUCTIONS ON SAMPLE COLLECTION AND USE OF INSTRUMENTS DETERMINATION OF T OTAL HARDNESS DETERMINATION OF CARBON-DI-OXIDE DETERMINATION OF P&M ALKALINITY DETERMINATION OF FREE ALKALINITY IN BOILER W ATER (STRONTIUM CHLORIDE METHOD) DETERMINATION OF SULPHITE

2. 3. 4. 5.

6.

FIG.1 METHOD OF COLLECTING SAMPLE FOR OXYGEN FIG.2 WINKLER FLASK FOR DISSOLVED OXYGEN DETERMINATION 7. 8. DETERMINATION OF DISSOLVED OXYGEN (MORE THAN 0.10 PPM) DETERMINATION OF PERMANGANATE NUMBER (DETERMINING ORGANIC SUBST ANCES : POTASSIUM PERMANGANA TE CONSUMPTION) DETERMINATION OF EV APORATION (T .D.S) IGNITION RESIDUES AND VOLATILE MATTER

9.

10. DETERMINATION OF OIL (FLUOROCARBON MA TTERS) 11. DETERMINATION OF pH-V ALUE 12. DETERMINATION OF CONDUCTIVITY (CONDUCTO BRIDGE METHOD)

FIG.3 HYDROGEN ION EXCHANGER OF PLASTIC FOR MEASURING CONDUCTIVITY 13. DETERMINATION OF DISSOLVED OXYGEN 14. DETERMINATION OF SOLUBLE SILICA 15. DETERMINATION OF TOTAL SILICA 16. DETERMINATION OF ORTHOPHOSPHATE 17. DETERMINATION OF IRON - BATHO PENANTHROLINE METHOD

18. DETERMINATION OF COPPER NEOCUPROINE METHOD 19. DETERMINATION OF AMMONIA 20. DETERMINATION OF HYDRAZINE 21. DETERMINATION OF CHLORIDE (COLORIMETRIC METHOD) 22. DETERMINATION OF MORPHOLINE 23. DETERMINATION OF CYCLOHEXYLAMINE 24. DETERMINATION OF SODIUM (FLAME PHOTOMETER) 25. DETERMINATION OF SODIUM-LOW LEVEL (ONLINE METHOD)

INTRODUCTION

The operation of modem steam generating plant necessitates constant supervision of water and steam conditions. For effective supervision, examination of water and steam samples is essential to provide suitable data for those responsible for operating water treatment plant and steam generating units to enable them to form a picture of the general operational state.These data should also help to give timely warning of any changes to enable corrective measures to be taken before trouble or damage ensues. Collection of representative sample and use of correct method of measurement are vital to obtain accurate results. The frequency of sampling and analysis depends on the maximum time during which lack of knowledge of the concentration of contaminants or additives, is acceptable. Local conditions such as plant design, condenser leakage, blow down and startup will often dictate the sampling frequency. In order to that the measurement of a contaminant or additive can be capable of detecting the smallest significant deviation from a set standard, the precision of analytical results must not exceed given values. Therefore, analyst must make regular checks to ensure that the precision remains satisfactory; a statistical assessment of results is necessary. Auto - analysers are of benefit, as they give a better overall picture and reveal trends towards change. All automatic analytical instrumentations should be maintained in an operational and calibrated status. If chemical auto-analysers are not operational, greater emphasis must be placed on laboratory analyses. In general, major operational decision will be made on the results of these measurements to achieve optimum plant operation; in other words, the longest possible service life for the plant with minimum operational losses and consumption of chemicals.

1.

GENERAL INSTRUCTIONS ON SAMPLE COLLECTION AND USE OF INSTRUMENTS

1.1. SAMPLE COLLECTION - PRECAUTIONS In the conditioning of industrial water it is necessary that analyses be made to govern the treatment processes. If the results obtain from a analysis are to be of any value, it is necessary to get a sample that if freely representative of the condition of the water at the point at which the sample has been collected. Sampling lines are to be kept continuously flowing. Sampling and cooling water line should be free from choking and sampling lines to be purged for about 30 minutes every day as a routine and whenever choking is suspected. To avoid contamination of cooled samples they are to be collected in dust-free atmosphere. Cooling water contamination of samples is to be prevented. The sampling rate should be not less than 450 ml / min and sample temperature shall not exceed about 40 degree C. The container used for collecting samples should be made of polythene with innercap. Before collecting samples, rinse the container atleast 3 times. After collecting the samples, rinse the stopper and tightly close the container. 1.2 i) USE OF INSTRUMENTS - GENERAL INSTRUCTIONS Spectrophotometer :

The following instructions shall be followed to ensure the accuracy of Spectrophotometric determinations. a) The Spectrophotometer used for colorimetric determinations is to be calibrated atleast once in six months. The temperatures of both sample solution and calibration solution shall be nearly equal preferably about 25 degree C. Optically matched cells are to be used for calibration and measurement. For the determinations of the various parameters, individual graphs are to be prepared with standard solutions. The graphs are to be checked or redrawn if required during calibration checks. The straight line portion of the curve which represents linearity only is to be used. Solutions of higher concentrations are to be diluted suitably so that the concentration can be measured within the linear portion of the graph. Suppliers operating instructions shall also be followed. Other Instruments : The general operating instructions supplied along with instruments shall be followed.

b)

c) d)

e) f)

g) ii)

2.

DETERMINATION OF TOTAL HARDNESS

2.1 INTRODUCTION i) Total Hardness Calcium and magnesium ions in water are sequestered by the addition of sodium ethylene diamine tetra acetate. The end point of the reaction is detected by means of an indicator, chrome-black T, at an optimum pH of 10.0-10.4 which has wine red colour in the presence of calcium and magnesium, and a blue colour when they are sequestered. ii) Calcium Hardness Calcium ions in water are sequestered by the addition of EDTA. The end point of the reaction is detected by means of an indicator, murexide which is dark purple in the absence of calcium but with which calcium forms a light salmon red complex. The optimum pH range is about 10.4 2.2 REAGENTS i) Standard Calcium Chloride Solution (1 ml equals 1 mg CaCO ) 3 Dissolve 1.0000 g of reagent grade calcium carbonate containing less than 0.04% Mg (dry at 1100 C for one hour) in 10 ml 1: 1 hydrochloric acid without spattering, dilute exactly to one litre and transfer to a clean dry glass stoppered bottle for storage (or use a commercially prepared standard.) ii) Buffer Solution 350ml Ammonium hydroxide(conc.) + 54gms ammonium chloride + 20ml magnesium complex solution are mixed and made upto one litre with distilled water.(Magnesium solution is prepared as follows. 4.1 gm of MgO (analar) is mixed with 37.2 gms of EDTA and dissolved in 410 ml of warmed distilled water.) iii) Calcium indicator Grind 0.2 gm of Ammonium purpurate(Murexide) with 100gms of Sodium chloride to 40 to 50 mesh size. iv) Chrome Black T indicator Grind 0.2gms of chrome black T powder with 80gms of powdered NaCl and store in a dark coloured bottle.

V)

Standard EDTA Solution Di-sodium dihydrogenethylene- diaminetetra-acetate of analytical reagent quality is dried at 800C. Weigh 4.0 gm of the substance and dissolve it in 800 ml of demineralised water. Adjust the pH to 10.5 with 5% NaOH solution. Pipette 25 ml of the standard Calcium chloride solution (prepared above) into an Erlenmeyer flask (125 ml) . Add 1:4 Ammonia of Chrome-black T indicator.Titrate with the EDTA solution as per the procedure given below (2.4). Let V be the volume of the standard EDTA solution required for the titration. Volume of EDTA to be taken up for dilution = V/25 x 1000. The volume of EDTA solution as calculated above is taken in a 1000 ml. volumetric standard flask. Dernineralised water is used to make up to the mark in the volumetric flask. This EDTA solution corresponds to a value of 0.02N. The solution is stored in polythene bottles and restandardised monthly. Sodium hydroxide solution(4%) Dissolve 4.0 gms of NaOH in water and dilute to 100ml.

2.3

GLASSW ARES Burette (0. 1 ml accuracy) 50ml measuring cylinder-1No. White porcelain casserole with a glass stiffer.

2.4

PROCEDURE i) Total Hardness Pipette 50m l of the sample into a white porcelain casserole. If necessary adjust to pH 7-10 by using ammonium hydroxide or HCL Add 0.5ml of buffer solution and mix by stirring. (The pl-I of this solution should be between 10- 10.2). Add approximately 0.2gms of dry chromeblack T indicator to produce the required depth of colour. The titration with EDTA should proceed immediately upon addition of the chrome blackT. If hardness is present the solution will turn red. Standard EDTA solution is added slowly with continuous stirring until the end point is reached which is pure blue colour with no reddish tinge remaining. Further addition of EDTA will produce nofurther colour change.

ii)

Calcium Hardness Pipette 50ml of the sample into a white porcelain casserole. Add 2 ml of 4% NaOH solution and stir.(The pH of this solution should be above 10.4) Add approximately 0.2gm of calcium(Murexide) indicator. Add standard EDTA solution slowly with continuous stirring until the colour changes from salmon pink to orchid purple.

iii)

Calculation Total Hardness (as ppm CaC03) Calcium hardness (as ppm CaC03) = = ml std EDTA soln x 20 ml std EDTA soln x 20 Total hardness (as ppm CaC03) minus calcium hardness (as ppm CaC03)

Magnesium hardness(as pprn CaC03) =

3.

DETERMINATION OF CARBON -DI-OXIDE

3.1 INTRODUCTION The carbon di-oxide content is the sole contributor to the acidity of the water. On this account, the CO2 determination bears a close resemblance to the acidity titration. The differences reside in the concentrations of the titrants and the fact tha t the titration is conducted in a manner that minimizes the escape of the volatile CO2 gas. 3.2 REAGENTS i) ii) iii) Boiled distilled water-This should be used in the preparation of all solutions. Phenolphthalein indicator solution. 0.02 N sodium carbonate solution.

(Prepare 0.1 N Na2 CO3 solution by dissolving 5.3 g anhydrous Na2 CO3 in one litre of boiled distilled water. This solution should be diluted suitably to get 0.02 N Na2 CO3 solution) 3.3 EQUIPMENT Glass flask with 100 cc and 200cc marks. Burette-50cc capacity with 0. 1 ml marking

3.4

ANALYSIS PROCEDURE The water is run slowly for a long time through a hose reaching down to the bottom of the test flask. After pouring-off excess water down to the 100 ml mark or 200 ml mark, the content of free CO2 is determined at once on the spot. Add to the water I cc of phenolphthale in solution and titrate with 0.02 N Na2CO3 Solution. After each fresh addition of Na2CO3 solution, the flask is closed and turned upside down (Not shaken) before continuing. Titration is completed when the colour of the water stays weak pink for 5 minutes. In a second test the full quantity of sodium carbonate solution needed is added at once, and if necessary a little more, until the pink colour is retained for 5 minutes.

3.5

CALCULATION CO2 milli-grams per litre Where A N = A x N x 22000 / ml.sample taken

= milliliters of titrant used = normality of titrant

4. DETERMINATION OF P AND M ALKALINITY

4.1 THEORY OF TEST This test is based on the determination of the alkaline content of a sample by titration with a standard acid solution. In this measurement, the end-points are taken as points of change in the colour of organic indicators; phenolophthalein (apporx.pH 8.3) and methyl orange(approx. pH represent definite points to which the alkalinity of the sample has been reduced by the addition of the standard acid solution. 4.2 REAGENTS i) ii) iii) iv) 4.3 Sulphuric acid, N/50 Phenolphthalein Indicator Methyl orange indicator Methyl purple indicator

APPARATUS REQUIRED 1 1 1 1 Burette, 25ml or Casserole, porcelain, 250ml Cylinder, graduated, 50ml. Stirring rod, glass.

4.4

PROCEDURE FOR TEST Measure a clear 50 ml sample of water in the graduate and transfer to the casserole. Add 4 or 5 drops of phenolphthalein indicator. If the sample is an alkaline water, such as usually is the case with the boiler water, it will turn red. If the sample is a raw or natural water, it usually will remain coloureless. Add the standard N/50 sulphuric acid from the burette drop by drop to the sample in the casserole, stirring constantly until the point is reached where one drop removes t he last trace of red colour and the sample becomes colourless. Stop and record the total number of ml to this point as the P reading. Add 4 drops of methyl orange indicator (if no red colour develops on the addition of the phenolphthalein indicator to the original sample, the titration may be started with the methyl orange indicator at this point). Continue adding the acid drop by drop until one drop changes the colour from a yellow to a salmon-pink., Record the final burette reading as the M reading. This is a more difficult point and some practice may be required. The general tendency is to add too much acid. If too much acid is added, the sample will change from a salmon-pink to a definite red.Record the titration to the P point and the total titration to the M point as the P and M readings respectively. (Note that the M Reading will always be greater than the P reading in as much as the P reading is included in the M reading). If the water sample is coloured, such as one containing chromate, methyl purple indicatormay be substituted for methyl orange indicator to provide a more definite end-point. The color change with methyl purple is from green to gray to purple. The end-point is taken as the first change to a definite purple.

4.5

CALCULATION OF RESULTS Formula: ppm alkalinity as CaCO3 = ml N / 50 sulphuric acid x 1000 / ml.Sample

4.6

LIMITATIONS OF TEST It is preferable to expresses the results of the alkalinity determination in terms of P and M alkalinity as above.However, results are sometimes calculated in terms of bicarbonate, carbonate and hydrate on the assumption that titration to the P end-point is equivalent to all the hydrate and one half the carbonate alkalinity and that the titration to M is equivalent to the total alkalinity. Many factors such as the presence of phosphate silica, organic and other buffers affect this titration and the calculation of the form of alkalinity present may be in error. Under normal circumstances in plant control, expression of results as P and M alkanity is entirely satisfactory and is to be preferred from the standpoint of simplicity.

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4.7

ALKALINITY RELATIONSHIP The following table summarises the relationship between P and M values and the concentration of hydroxide, carbonate and bicarbonate. ppm as CaCO 3 Condition P=O 2P<M 2P=M 2P>M P=M (OH) (OH - ) O O O 2P-M M (CO3)(CO 3-) O 2P 2P 2(M-P) O (HCO3) (HCO3-) M M-2P O O O

5.

DETERMINATION OF FREE ALKALINITY IN BOILER WATER (STRONTIUM CHLORIDE METHOD)

5.1 INTRODUCTION This method is based on the titration of the hydroxide ion with a standard acid to the Phenolphthalein end-point after the carbonate and phosphate ions have been precipitated with strontium chloride. 5.2 REAGENTS i) ii) iii) Standard HCI solution 0.02 N Phenolphthalein indicator dissolve 0.5g of phenolphthalein in 100ml of 50% solution of ethyl alcohol in water Strontium chloride solution = Dissolve 4.5g of strontium chloride in water and dilute to a litre.

5.3 APPARATUS REQUIRED 50 ml - measuring cylinder 250 ml - Erlenmeyer flask with stopper 50 ml - burette-readability 0.1ml

11

5.4

PROCEDURE Pipette 50 ml of sample into 250 ml. Erlenmeyer Flask. Add 25 ml of stroniurn chloride solution Keep loosely the stopper of the flask and heat to boiling. Remove flask and immediately push stopper tightly into flask. Allow to cool and add 5 drops of phenolphthalein solution. The absence of colour indicates no free hydroxide alkalinity. If pink colour is present, titrate with 0.02 N hydrochloric acid to a colourless end-point.

5.5

CALCULATION Free alkalinity as ppm (OH) Where, = (N) x (V) x 17,000 / ml sample

V = ml of HCI and N = Normality of HCl

5.6

INTERFERENCES Chromates and Silicates Method takes care of phosphates, carbonates and most ammonia.

6. DETERMINATION OF SULPHITE
6.1 INTRODUCTION This method is designed primarily for the routine control of boiler feed waters subjects to sulphate treatment. Reductants like sulphide and certain heavy metal ions react similarly to sulphite. Copper catalyzes the oxidation of sulphite on exposure to air, especially at high temperatures. 6.2 REAGENTS i) Standard Potassium Iodate

ii)

Dissolve 0.566 g KI03, dried at 1200C, and 0.5 g NaHC03 in distilled water, and dilute to 1000 ml. The equivalence of this titrant is 1.0 mg Na2 SO3 per 1.00 ml.

12

iii)

Potassium Iodide Solution, (50 g per litre)-Dissolve 50 g of iodate-free KI and 0.5g of sodium bi-carbonate (NaHC03) in freshly boiled and cooled water and dilute to one litre. Starch indicator. Hydrochloric Acid, 1 +1

iv) v)

6.3

APPARATUS REQUIRED 250 c.c erlemneyer flask 10 c.c pipette ( for 1:1 HCl ) 100 ml pipette (for the sample to be measured) 5 ml pipette ( for the sample to be measured ) 1 ml burette ( for KIO 3 titrant)

6.4

PROCEDURE Place 10 ml 1 + 1 HCl in a 250 ml flask. Rapidly add 100 ml. sample, submerging the pipette tip below the acid surface to minimize air exposure. After adding I ml. starch indicator solution and 5 ml KI solution, titrate ivith standard KI03 titrant to the first appearance of a persitent blue colour. Determine the blank titration by carrying 100 ml. distilled water through the complete procedure. SO3 milligrams per litre = (A-B) x 6.35

Na2 SO3 milligrams per litre = (A-B) x 10 Where A = B = millilitres of titration for sample. millilitres of titration for blank.

13

FIG.1 METHOD OF COLLECTING SAMPLE FOR OXYGEN DETERMINATION ON HOT FEED WATER

FIG.2 WINKLER FLASK FOR DISSOLVED OXYGEN DETERMINATION

14

7.

DETERMINATION OF DISSOLVED OXYGEN (MORE THAN 0.10 PPM)

7.1 SAMPLING It is important to use air-tight connections in all apparatus used for sampling and testing. When sampling hot water, a water cooled coil should be introduced into the sampling line. A convenient arrangement for sampling for feed water is shown in the figure. The sample itself should be taken in a 500 ml. Winkler flask, containing a few glass beads, as shown in figure and water should flow through for atleast 10 minutes before taking the actual sample so as to displace all traces of air. Care must be taken to see that air bubbles do not form around the stopper of the Winkler flask while sampling. 7.2 REAGENTS REQUIRED i) Manganous chloride Dissolve 400gms of Manganous chloride(AR) in one litre of DM water. ii) Alkaline iodide Dissolve 600 gm of potassiumhydroxide and 140gm of potassium iodide in 1litre of water. iii) N / 100 Sodium thiosulphate Dissolve 2.482gm of AR Sodium thiosulphate(Na2S2O25H2O) in water and make up to one litre. Add about I gm of AR Sodium carbonate to preserve the solution. Standardise against standard potassium dichromate. iv) Sulphuric Acid 1:1 Add 250ml of conc.sulphuric acid to 250 ml of water. Cool and store. 7.3 GLASSW ARES Winklers flask arrangement as shown in the figure. 2ml pipette Burette 50 ml - 1 No. 7.4 PROCEDURE By means of the funnel fitted to the Winklers flask, add 2 ml of the manganous chloride solution and then add 2 ml of the alkaline Iodide soldtion. Mix, allow to stand for 10 minutes and then add 2 ml of 1:1 H2 SO4. Take 250 ml of the sample and titrate the liberated iodine with N/100 Thiosulphate solution using starch as indicator.

15

ML of Oxygen / Litre = ML of N/100 Thio used x 0.224 1 ML of Oxygen / Litre = 1.430 Mg / Litre

8. DETERMINATION OF PERMANGANATE NUMBER (Determining organic substances : Potassium Permanganate Consumption)

8.1 OXYGEN CONSUMED FROM PERMANGANATE Two versions of the oxygen consumed from permanganate method are in the use for estimating the strength of organic pollution in streams. One modification hastens the oxidative reaction by elevating the sample temperature over a shorter time. The other determination is conducted near room temperature for an extended period. Since both procedures are empirical, experimental conditions must be uniform for the results to have significance. Clean glassware is mandatory. 8.2 REAGENTS i) Standard potassium permanganate solution, 0.0125 N-Filter the supernatant from an aged solution of 0. 1 N KMnO 4 through sintered glass crucible, and dilute 12.5 ml to 100 ml withdistilled water. Standardize the solution daily. The equivalence of 0.0125 N KMnO 4 is 0.100 mg oxygen consumed per 1.00 ml. Sulphuric acid solution,1 + 3 - Add 0.0125 N KMnO 4 solution until a very faint colour persists after 4 hours. Sodium sulphide dechlorinating solution, 0.025 N 1.575 g per 100 ml. ii) Reagents for Half-hour method Standard Ammonium oxalate titrant, 0.0125 N Dissolve 0.8882 g. (NH4)2 C2O4. H2O, dried at 105o C and dilute to 1000 ml with distilled water. iii) Reagents for pour hour method Standard sodium thiosulphate titrant, 0.0125 N. In a 1 litre volumetric flask place 0.6 g NaHCO3 and dilute 12.5 ml 0.1 N Na2S2O3 with distilled water, Prepare daily and standardize. Starch Indicator. Potassium Iodide.

16

8.3

PROCEDURE When the residual chlorine exceeds 0.5 mg per litre, dechlorinate the sample with a minute amount of 0.025 N Na2SO3 solution to the 0.65 mg per litre level. Do not dechlorinate completely. i) Half hour method Pipette 100 ml well-mixed sample and 100 ml distilled water into separate 250 ml flasks, and treat both the sample and blank alike throughout the procedure. Add 10 ml (1+3) H 2 SO4 and 10.00 ml standard 9.0125 N KMnO 4 . Immerse the flask in a boiling water bath for exactly 30 min. making certain that the liquid level in the flask is completely submerged in the boiling water throughout- the entire period. If the KMnO4 colour in the sample grows faint or disappears, take a smaller volume and dilute to 100 ml standard 0.0125 N (NH4 )2 C2 O4 solution, and while still hot, titrate with standard 0.0125 N KMnO 4 to a faint pink end-point. Oxygen consumed from KMnO4 milligrams per litre = (A-B) x N x 8000 / millilitres of sample

Where

A B N

= Millilitres of titration for sample = Millilitres of titration for distilled water blank, and = Normality of KMnO4 titrant.

(ii)

Pour- hour method Measure 250 ml well mixed sample and 250 ml distilled water into separate 400 ml glass stoppered bottles, and bring to 27C. Treat both the sample and blank alike throughout the procedure. Add 10 ml (1+3) H2 SO4 with a volumetric pipette introduce an appropriate volume of standard 0.0125 N KMn04- Select a KMnO 4 volume in sufficient excess to require a back-titration of 5 to 15 ml at the end of 4 hour and in any case, use no less than 10.0 ml KMnO 4 . Gently rotate the bottle to mix the contents, and place in a water bath or incubator at 27C for exactly 4 hours. Several times during the incubation, mix, by gentle rotation, anysample that contains appreciable suspended matter. Cool to room temperature and a few small crystals KI,mix, and titrate the contents of the bottles with standard 0.0125N Na2S2O3 titrant. Add 1.0 ml starch indicator when the colour turns pale straw, and complete the titration to the first disappearance of the blue colour.

17

9.

DETERMINATION OF EVAPORATION (T.D.S.) IGNITION RESIDUES AND VOLATILE MATTER

9.1 EVAPORATION RESIDUES AT 105C i) Apparatus required 200 c.c Capacity platinum evaporation dish 100 c.c & 200 c.c Pipettes to measure water to be tested Water bath Drying oven Desiccator Ignition furnace ii) Procedure 100 c.c or possible a greater quantity of water to be tested (filter if suspended solids are present - estimate separately suspended solids content) is evaporated in a platinum dish on a water bath until it is dry, after which it is dried down, to constant weight in a drying oven at 105C. It is weighed after cooling in the desiccator. 9.2 DETERMINING THE IGNITION RESIDUES The evaporation residue determined at 105C as described above is ignited in an ignition furnace at 600 + 25C until constant weight. Cool in the desiccator and weigh. Constant weight shall be considered as attained when the change in weight of the dish plus residue shall not be > 0.5 mg between two successive operations involving heating, cooling in a desiccator and weighing. 9.3 DETERMINING THE VOLATILE MATTER Record the loss in weight in the previous determination as weight of volatile dissolved matter. 9.4 CALCULATIONS Total dissolved solids Ignition residue Volatile matter Where A B (A-B) W = = = = ppm A/W x ppm B/W x ppm (A-B) / W x 1000 1000 1000

gms of dissolved matter gms of ignition residue gms of volatile matter ml / weight of sample used

18

10. DETERMINATION OF OIL (Fluorocarbon matters)

10.1 INTRODUCTION In the determination of oil, an absolute quantity of a specific substance is not measured. Rather,group of substances with similar, physical characteristics are determine quantitatively on the basis of common solubility, in specified solvent. The constituent analysed may therefore be said to include hydrocarbons, fatty acids, soaps, fats, waxes, oil and any other material that is extracted by the solvent form an acidified sample. 10.2 REAGENTS Acetone Hydrochloric acid Sodium bisulphate. (NaHSO4 H2 0) Sodium chloride Sodium sulphate (Na2 SO4 ) Sulphuric acid Fluorocarbon solvent (1,1,2-Trichloro-1,2,2-Trifluoro ethane) 10.3 APPARATUS Drying oven Evaporating flask Separatory funnel Steam bath Desiccator 10.4 PROCEDURE Dry a boiling flask in an oven at 105o C for lhr and cool in a desiccator. Weigh accurately, (W1 g). Collect the sample in a glass container. Note the volume. Add HCl (1:9) dropwise and adjust the pH to 3.0 & 4.0 pour the acidified sample into a separatory funnel.Add 60 ml. of fluorocarbon solvent to the glass container in which the sample is collected. Cap and shake the bottle well. Pour the solvent into the separatory funnel. Extract the sample by shaking vigorously for 2 minutes. Invert the separatory funnel and vent with stopcock to relieve pressure built up during the extraction. Allow the layers to separate. Drain the solvent layer through filter paper (whatman) held by a small funnel- into the tared boiling flask. (if emulsion problems are anticipated, add 1 to 2g of sodium sulphate to the filter paper cone and slowly drain t he solvent through the crystals, If a clear solvent is not obtained, add about 100g of sodium chloride to the separatory funnel. Frequently this will break the emulsion).

19

Repeat the bottle rinse and extraction with two additional 60ml portion of the solvent. combine all the solvents in the same boiling flask.Rinse the filter with 20ml of the solvent into the same flask.Evaporate (in a fume hood) the solvent from the boiling flasks in a steam bath. When the contents have been evaporated to dryness, (without any solvent vapour or residual water), carefully wipe the exterior of the flask with a lint free cloth and a small amount of acetone to remove any water adhering to the flask. Place in a desiccator for 1 hr and weigh (W2 g) 10.5 CALCULATION Extractable residue (mg/litre) = (W2-WI) x 1000 / ml.sample

11. DETERMINATION OF pH-VALUE

11.1 INTRODUCTION As a yard stick for the concentration of hydrogen ions, the pH value gives an indication of the percentage reaction (alkalinity or acidity) of the water and hence its aggressive nature. The pH value is the negative logarithm to the base 10 of the hydrogen ion concentration, expressed as gram-ions per litre. The pH value of a given solution depends on the temperature and as a rule it is quoted for 250 C. Water with pH = 7 has a neutral reaction, while there is an acidic reaction at pH<7 and a basic reaction at pH >7. 11.2 APPARATUS REQUIRED pH meter with Associated glass and reference electrodes. Buffer tablets of known pH. 11.3 ELECTROMETRIC DETERMINATION OF PH V ALUE With the electrometric method, the pH value is determined from the potential difference between the measuring electrodes immersed in the liquid under test and a reference electrode of known potential. For testing water, electrode assemblies comprising a glass electrode and a calomel reference electrode are suited. pH meter is to be operated in accordance with the instruction supplied with it, by its manufacturer. Where water is very pure, and the pH value and electrical conductivity are being determined simultaneously, make sure that the pH electrodes are inserted. After the conductivity electrodes if the measuring points are connected in series.

20

11.4

ELECTRODE TREATMENT New glass electrodes and those that has been stored dry shall be conditioned and maintained as recommended by the manufacturer. If the assembly is in intermittent use, keep the immersed ends of the electrodes, in water between measurements. For prolonged storage, glass electrodes may be allowed to become dry, but the junction and filling openings of reference electrodes should be capped to reduce evaporation.

11.5

STANDARDISATION OF ASSEMBLY Turn on the instruments, allow it to warm up and bring it to electrical balance in accordance with the manufacturers instructions. Wash the glass and reference electrodes and the sample cap by means of a flowing stream of distilled water from a wash bottle. Note the temperature of the test solution and adjust the temperature dial of the meter to correspond. Select the two reference buffer solutions, near the pH of the test solution. (Buffer solutions can be prepared from the buffer tablets following manufacturers instructions). Warm or cool these reference solutions as necessary to match within 20 C the temperature of the unknown. Fill the sample cup with the first reference buffer solution, and immerse the electrodes.Engage the operating button, turn the range switch if present to the proper position, and rotate the assymmetry potential knob until the reading of the dial corresponds to the known pH of the reference buffer solution. Repeat the above procedure until two successive instrument readings are obtained, without changing the setting of the asymmetry potential knob. Care should be taken to see that the level of the KCIsolution in the referencce electrode must always be kept more than that of the measured solution. To reduce the effects of thermal and electrical hysteresis, the temperature of electrodes reference buffer solutions and wash water should be kept as close to that of the unknown sample as possible. Wash the electrodes and sample cup three times with water. Place the second reference buffer solutions in the sample cup, and measure pH. Do not change the setting of assymmetry potential knob. The assembly shall be judged to be operated satisfactorily if the pH reading obtained for the second reference buffer solution agrees with its assigned pH value within 0.05 unit.In long series of measurements, supplement initial and final standardisations by interim checks. Wash the electrodes by means of a flowing stream from a wash bottle. Place the water sample in a clean glass beaker. Measure the temperature. Insert the electrode and measure pH as before.

11.6

INSTRUCTIONS pH meter should be checked Periodically for its performance using buffer.

21

12. DETERMINATION OF CONDUCTIVITY (Conducto Bridge Method)

12.1 CONDUCTANCE (SPECIFIC) The specific conductance of water is a measure of the ability of the water to conduct an electrical current. This property is of no consequence in itself with respect to water treatment. However, from a control stand point, the conductivity test is important as a direct measure of the total ionizable solids in the water. The conductivity test provides quick measurement of steam purity as well as a simple control for boiler water solids. Conductivity also may be used for blowdown control in recirculating cooling water systems. Specific conductance is inversely proportional to electrical resistance. Pure water is highly resistant to the passage of an electric current and therefore has a low specific conductance. However, if the water contains ions, the water becomes a better conductor of electricity and the specific conductance is increased. Inorganic compounds such as sodium chloride and sodium sulphate dissociate into positive and negative ions, which will conduct electricity in proportion to the amount of ions present. The conductivity test, therefore, is not specific for any one ion, but rather a measure of the total ionic concentration. The basic unit of electrical resistance is the ohm. since electrical conductivity is the reciprocal of resistance, the unique term mho (ohm spelled backwards) was chosen as the basic unit of conductivity. In the conductivity test, small amounts of electrical conductance are measured and the instrument is usually calibrated in micromhos (a micromho is a millionth of a mho). To calibrate a conductivity instrument to read directly in parts per million of dissolved solids (or some specific ion or compound) is not recommended since such a calibration introduces an error into the instrument reading itself. The conversion factor from micromhos of specific conductance to parts per million will vary slightly with different waters. To include a constant conversion factor in the instrument calibration is to introduce an unnecessary source of error. The conductivity test provides an accurate and simple method of blowdown control. However, certain limitations must be considered. While the conductivity test measures the total ionic concentration, the hydroxide ion has a much higher conductance than the other ions present.Thus for accurate results the sample must be neutralised before the conductivity test is made. Conductivity is an exceedingly sensitive test and is accurate down to the level of approximately 0.5 - 1.0 ppm ionizable solids. Until development of the flame Spectrophotometer method for determining low sodium concentrations, conductivity was the most accurate method of determining steam purity. 12.2 APPARATUS REQUIRED 1-Conducto Bridge (0-5 to 0-5000 micro mho/cm with selector switch) 1-Dip cell 1-Cylinder, rimmed glass, not graduated 1-Thermometer, dial type (0- 100C) 1-Measuring cup , brass 22

12.3

CONDUCTANCE OF BOILER W ATER Theory of test: The ionizable solids in boiler water have the ability to conduct an electric current through a solution. This property of electrical conductance of solids makes it possible to accurately measure the quantity of solids in solution by suitable conductance equipment.

12.4

CHEMICAL REQUIRED. Gallic Acid

12.5

PROCEDURE FOR TEST Pour approximately 50 ml of distilled water or steam condensate into the rimmed glass cylinder and insert the conductivity cell. Move cell up and down several times to wash off any solids present on the cell. Discard the water in the cylinder. Pour approximately 50 in of boiler water into the cylinder (use a settled or filtered sample), Add two dippers of gallic acid (approx. 0.2 g) to the sample. (Note: if a small amount of the gallic acid remains undissolved, the conductivity test will not be adversely affected). Measure temp of the sample and adjust the temperature correction dial on the conducto Bridge to the proper temperature. Insert conductivity cell and move up and down several times to insure equilibrium. Measure the specific conductance on the Conducto Bridge by turning the conductivity dial until the electric or magic eyes is at its widest black angle. Note: Two dippers of gallic acid will neutralize approximately 130 ppm of P alkalinity. On some highly alkaline boiler waters, additional gallic acid may be required. A desirable precaution is to add approximately four drops phenolphothalein indicator to the sample and delay taking the conductivity reading until the pink colour has been completely discharged by the addition of gallic acid.

12.6

CALCULATION OF RESULTS The specific conductance in micromhos is read directly from the calibrated scale as indicated by the pointer on the conductivity knob, when the eye is at its widest black angle. The relationship between specific conductance and the dissolved solids content of a boiler water depends on the characteristics of each individual boiler water and therefore may be slightly different for each plant. Using the gallic acid neutralization method, an average value determined over a wide range of operating conditions is that one micromho is equivalent to 0.9 pprn dissolved solids. This value is sufficiently accurate for the average industrial plant.

The exact relationship between micromhos and solids can be individually established for each plant by determining both the conductance and solids content of a series of approximately ten sample taken over a two week period.

23

12.7

LIMITATIONS OF TEST The conductance method affords a rapid means of checking the dissolved solids content of a sample. The effect of hydroxide in causing high conductivity is minimized by the gallic acid neutralisation, thereby securing a consistent relationship between solids and conductance. The conductance method does not measure non-electrolytic solids such as organic matter, and in order to express results in terms of parts per million of boiler water solids it is necessary to use a conversion factor.

12.8 i)

CONDUCTANCE OF STEAM CONDENSATE AND FEEDW ATER Theory of test The ionizable solids and gases in condensed steam and feed water have the ability to conduct an electric current through a solution. In evaluating the conductance of condensed steam and feed water samples, it is necessary to check for the presence of dissolved gases such as ammonia and carbon dioxide which impart conductance. The effect of ammonia is predominant and hence the sample is allowed to pass through a cation resin column (in H form). An arrangement of resin column is shown figure 1. Ammonia is removed by this method and. the conductivity measured will indicate the dissolved solids present.
+

The solids are converted to their corresponding acids by passing the sample through the cation column and the approximate conductance of acids to ppb relationship can be as follows: Weak acids (H2 CO3 ,HAC =0.004 mmho/ppb (as CaCO3 ) Strong acids (HCl, H2 SO4 , HNO3 ) =0.007 mmho/ppb (as CaCO3 ) Cation conductivity measuring less than 0.3 micromho/cm will mean total solids in the sample less than 50 ppb. ii) Procedure for the test Collect approximately 50 ml of the condensed sample after passing through the cation column (in the H+ form). The effluent sample is measured for its conductivity. For measuring conductivity above 10 micromho/cm, either a flow type or dip type cell may be used. For samples with conductivity below 10 micromho/cm flow type conductivity cell tube used. Adjust the sample stream to proper flow rate and temperature.(250 C). Read the conductance by continuous (on-line) measurement.

24

iii)

Regeneration procedure for cation column The cation resin in the H+ form when exhausted should be regenerated as per the procedure described below:

iv)

Backwards flushing To remove contaminations, first shake the cation exchange thoroughly by hand then allow condensate to flow through from the bottom upwards for about 5 minutes until the discharge rinsing water is clear and colourless. Watch that no resin is flushed out.

v)

Regenerating For regenerating the exchanger resin allow 6 litres of technical hydrochloric acid 1:4 diluted with condensate per I litre of resin to flow through the apparatus from the top downwards for at least 30 minutes. (Flow rate approximately 8- 10 litres/hr.) There must be no air bubbles on the bottom of the sieve, since these inhibit the flow and affect the regeneration. The discharge is strongly acidic and must only be emptied into an acidresistant drain.

vi)

Flushing-out For 30 to 40 minutes in any case until the Cl-reaction (check with AgNO3 ) has disappeared flush-out the remaining acid in the apparatus with condensate from the top downwards. Flow rate 20- 30 litres/hr.

vii)

Start-up Before starting up again check once more to see whether there is any air bubbles on the bottom of the sieve: otherwise, the cation exchanger will operate irregularly and inefficiently.

viii) Remarks If the exchanger resin is considerably contaminated with iron oxides or other deposits, the regenerating acid may be heated to 500 C and left for about half an hour in the resin before flushing. ( Temperature resistance of the resin: Max.1000 C ). Following this backwards flushing will have to be carried out again, if necessary, to remove any released particles from the resin. Resin contaminated with oil can be cleaned with. a detergent.

25

FIG.3 HYDROGEN ION EXCHANGER OF PLASTIC FOR MEASURING CONDUCTIVITY

13. DETERMINATION OF DISSOLVED OXYGEN

Colorimetric determination of low concentration of dissolved oxygen in water less than 0.10 ppm. 13.1 INTRODUCTION This method uses the dissolved oxygen in the sample to oxidise a reduced solution of indigo carmine. As the reduced solution of indigo carmine is oxidised, it changes colour progressively from yellow to orange to pink to red to purple to green. 13.2 REAGENTS i) Reagent solution About 30 minutes before testing, add 20 ml of indigo carmine solution and 5 ml of potassium hydroxide solution to a small beaker. Stir gently and pour into a 50 ml burette. ii) Indigo carmine solution Dissolve 0.018 gm of indigo carmine and 0.2 gm of dextrose in 5 ml. of boiled eionized water. Add 75 ml of glycerol and stir well. This reagent should be used within two weeks.

26

iii)

Potassium hydroxide solution Dissolve 100 gms of potassium hydroxide in 200 ml of boiled deionized water.

13.3

GLASSW ARES BOD bottle 300 ml capacity with grounded neck and stopper - I No. Burette (50 ml capacity) - 1 No. White porcelain tile - 1 No. The colours produced by mixing the coloured solutions given below can be used as reference for determining the dissolved oxygen content by indigo carmine test. i) Colour standards Stock solutions a. Red colour standard (CS-A) Dissolve 59.29 g of cobaltous chloride hexahydrate (COCl2.6H2O) in sufficient HCl (1 : 99) to make one litre. b. Y ellow colour standard (CS-B) Dissolve 45.05 g of Ferric chloride hexahydrate (FeCl3 6H2O) in sufficient HCl (1:99) to make one litre.

c.

Blue colour standard (CS-C) Dissolve 62.45 g of cupric sulphate pentahydrate (CUSO4 5H2O) in sufficient HCl (1:99) to make one litre.

ii)

Store all stock solutions in dark-coloured bottles to prevent fading.

27

iii)

Preparation of colour standards Prepare a series of colour standards as listed in the following table:

Disolved Oxygen

Milliliters of colour standard

ppm 0.000 0.005 0.010 0.015 0.025 0.050

CS-A 0.75 5.00 6.25 9.40 14.4 18.3

CS-B 35.0 20.0 12.5 10.0 3.8 1.7

CS-C -------------

Place the amounts of stock solutions in the table in 300 ml borosilicate glass stoppered reagent bottles. Add 2.3 ml of HCl (sp.gr.1.19) to each and dilute to the neck of the bottle with water. Stopper the bottle and mix by inversion. Store in a dark place to minimise fading of colours.

13.4

PROCEDURE i) Attach a minimum length of rubber tubing tipped with about a 4" piece of glass tubing to the sample point. Insert the glass tubing to the bottom of the BOD bottle of 300 ml.capacity, having a raised lip around the neck and glass stoppers ground to a conical lower tip. Permit the sample to fill and overflow the bottle an equivalent of at least 10 times. The sample should be at room temperature or below. Remove the glass tipped rubber tubing slowly. Insert tip of the burette containing the reagent, below the neck of the bottle and add 4 ml of the reagent. Remove the burette, carefully stopper the bottle and shake well. Determine the colour immediately by placing the bottle in a white surface and view, looking into the bottle at 450 angle.

ii)

iii) iv)

V) vi)

28

ppm 0.000 0.005 0.010 0.015 0.025 0.050

Color Yellow Orange Orange pink Pink Pink red Red purple

14. DETERMINATION OF SOLUBLE SILICA

14.1 SUMMARY OF METHOD This colorimetric method depends on forming molybdi-silicic acid by reacting the silica and ammonium molybdate in acid solution. I-amino-2 napthol-4 sulfonic acid is then added to reduce the molybdi-silicic complex. The method is designed to determine soluble silica with high accuracy in the range of 5 to 1000 g/ litre [1g/litre =1 ppb.] 14.2 REAGENTS i) Amino - naptho l- sulfonic acid solution - Dissolve 0.5 g of 1-amino-2napthol 4- sulfonic acid in 50 ml of a solution containing 1 g sodium sulphite (Na3 SO3). After is solving, add the solution to 100 ml of a solution containing 30 g of sodium hydrogen sulphite (NaHSO3 ). Make up to 200 ml and store in a dark, plastic bottle. Prepare a fresh solution every 2 weeks. Ammonium molybdat e solution - (100 g/litre) Dissolve 10 grams of ammonium molybdate tetrahydrate in 100 ml of deionized water. Filter this solution each day before using. Hydrochloric Acid (1 + 1) - Dilute 1 volume of concentrated hydrochloric acid (HCl, sp. gr. 1.19) with I volume of deionized water. Oxalic Acid Solution - (100 g/litre) - Dissolve10 grams of oxalic acid dihydrate (H2 C2 O4 2H2 O) in 100ml. of deionized water. Silica, Standard solution (1 ml =1mg. Si02 ) - Dissolve 4.732 g of sodium metasilicate (Na2 SiO 3 9H2 O) in water and dilute to 1 litre. Check the concentration of this solution in accordance with Reference Method A. (ASTM 859). Silica standards may be purchased from several chemical supply houses. 29

ii)

iii)

iv)

v)

14.3

APPARATUS REQUIRED i) ii) iii) iv) v) vi) vii) 50 ml - pipette 250 ml - polyethylene container 1 ml pipette (for 1: 1 HCl) 2ml pipette (for ammonium molybdate solution) 2ml pipette (for oxalic acid solution) 2ml pipette (for ANS solution) Spectrophotometer

14.4

PROCEDURE i) ii) iii) iv) v) vi) vii) Pipette 50 ml of clear sample into a 250 ml polyethylene container Add I ml of 1 + 1 HCI solution Add 2 ml of ammonium molybdate solution Wait 5 minutes. The sample should be swirled during this period. Add 2.0 ml of oxalic acid solution. Swirl to mix wait for 2 min. Add 2.0 ml of I-amino-2-napthol-4 sulfonic acid solution and swirl. Wait 5 minutes. Read on spectrophotometer at 815 nm. Transmittance of the reagent blank versus deionized water should not be less than 98.8%

14.5

CALIBRATION Prepare a series of atleast 4 standards by proper dilution of the standard silica solution.Treat 50 ml aliquots of the standards in accordance with steps given under the procedure. (14.4) Prepare a blank using a 50.0 ml aliquot of DM water that has been similarly treated. Read the absorbance values from the spectrophotometer at 815 nm (A separate calibration curve in the wave length range of 640 to 700 nm can also be prepared but with less sensitivity)

14.6

CALCULATION Silica concentration of the unknown solution can be read directly form the calibration curve.

15. DETERMINATION OF TOTAL SILICA

15.1 INTRODUCTION Some boiler stations using ion exchange columns for preboiler water purification, have noticed silica concentrations building up in the units and at the same time a soluble silica analysis onwater coming from the ion exchange column showed no silica. Analysis for colloidal silica on these same samples showed the -silica was present as colloidal particle. This technique has been developed as an analytical procedure to accurately determine trace concentrations of silica where all or a part is present in colloidal form. Total silica is determined spectrophotometrically after solubilization by the pressurized bomb method. (Paar Oxygen Bomb). 30

15.2

APPARATUS REQUIRED -25 ml , 50 ml, 10 ml - pipette for suitable aliquot sample -Platinum cup with cover -Oxygen bom -1 ml pipette -10 ml -Pipette (for deionized water) -Nitrogen cylinder with pressure regulator, opener etc. -AIROVEN to be capable of giving a temperature 1900C. for 12 hours continuously - Spectrophotometer.

15.3

PROCEDURE i) ii) iii) Accurately measure 50 ml or a suitable aliquot of the sample into a platinum cup. Add I ml of 0.2 N NaOH and close the cup with a platinum cover Place the closed cup in a Paar oxygen bomb containing 10 ml of deionized water and completely assemble the bomb. Nitrogen is added to obtain 30 pounds pressure and let out five times to completely flush out oxygen in the bomb to prevent bomb corrosion. Pressurize the bomb with nitrogen to 45 psig (maintained for specified period) and place in an oven at 190o C for 8 hours. The oven should be placed in a hood since all gaskets in the bomb are made of Teflon. Remove the bomb from the oven, cool, and remove the sample from the platinum cup silica is determined spectrophotmetrically

iv)

v)

vi)

15. 4

CALCULATION i) ii) See silica curve for the spectrophotometer used. Colloidal silica (ppm) = Total silica (ppm) -Soluble silica (ppm).

16. DETERMINATION OF ORTHOPHOSPHATE

16.1 INTRODUCTION This method is applicable to the routine determination of orthophosphate in the 2 to 25 ppm PO4 range in industrial water and is based on the photometric measurement of the yellow colour of the molybdo vanadophosphoric acid produced. The colour intensity is proportional to the orthophosphate concentration in the sample. Highly coloured water such as tannin treated boiler water and high concentration of ferric iron interfere thus requiring preliminary treatment to remove these materials.

31

16.2

REAGENTS i) Ammonium vanadomolybdate solution - Dissolve 40 grams of ammoniummolybdate tetrahydrate (NH4 ) MO 7 O24 , 4H2 0) in 400 ml of water. Dissolve1.0 gram of ammonium metavanadate in 300 ml of water and add 200 ml concentrated nitric acid (Sp. Gr. 1.42). Add the first solution to the second solution, mix well, and dilute to one litre with water. Phosphate standard solution (1 ml= 1 mg PO4) -Dissolve 1.433 grams of oven-dried (4 hours at 1050 c). Potassium dihydrogen phosphate (KH3 PO4 ) in water and dilute volumetrically to one litre.

ii)

16.3

APPARATUS REQUIRED i) ii) iii) iv) v) 125 ml Erlenmeyer flask 50 ml , 25 ml , 10 ml pipette for suitable aliquot sample Filter stand with funnel, whatman No.42 filter paper etc. 25 ml graduate (for Ammonium vanadomolybdate solution) Spectrophotometer

16.4

PROCEDURE i) To a 125 ml Erlemneyer flask, add 50 ml of the clear sample or aliquot there of diluted to 50 ml with deionized water. Add, using a graduate, 25 ml of ammonium vanadomolybdate solution and mix well by swirling. Allow 10 minutes for colour development and read within 30 minutes on the spectrophotometer at 400 nm. Reagent blank and atleast two phosphate standards should be run along with samples.

ii)

iii)

iv) 16.5

CALIBRATION AND STANDARDIZATION Prepare a series of standards to cover the range of 25 mg / litre (ppm) and prepare calibration curve.

32

17. DETERMINATION OF IRON - BATHO PENANTHROLINE METHOD

17.1 INTRODUCTION This method covers the determination of total iron in the range of 0-200 ppb. This method is based upon the red ferrous complex produced by the bathophenanthroline and reduced iron. The addition of hydroxylamine hydrochloride reduces ferric to ferrous with the pH adjusted between 3.3 and 3.7 before extracting the complex with n-hexylalcohol. 17.2 SAMPLING Although samples may be taken in polyethylene bottles, it is recommended that meticulously clean 500 ml glass bottles with plastic caps be used. Prepare bottles by soaking in hot HCl (l +1) for several hours prior to use. Drain and flush several times with iron-free water. Add 1 ml of concentrated HCl to each 500 ml bottle and cap until used. When taking sample, be sure, sample point has been continuously running for atleast four hours. Do not overflow the acidified sample bottle during sample collection. 17.3 STANDARDS Prepare a series of iron standards in 250 ml. separatory funnels to cover the range expected. Use the iron std. solution (I ml=0.001 mg Fe). include a zero blank and follow procedure. 17.4 REAGENTS i) ii) iii) iv) V) Alcohol - lsopropyl Alcohol - n-hexyl Ammonium hydroxide (1 + 1) Hydrochloric acid concentrated and HCI (1+9) Bathophenanthroline solution (0.835 g/litre). Dissolve 0.0835 of 4,7 dipheny 1-1, 10-phenanthroline in 100 ml of ethyl alcohol (95%) Hydroxylamine hydrochloride solution (100 g/litre). Dissolve 10 g of NH2 OH HCl in water and dilute to 100ml. Purify as follows: Adjust pH to 3.5 using a pH meter by dropwise additions of NH2 OH(1+1) and HCl (1+9). Transfer to a separatory funnel. Add 6ml.of bathophenanthroline solution and shake. Let Stand for 1 minute. Add 20 ml of n-hexyl alcohol and shake for I minute. Let separate, remove aqueous layer and discard alcoholic layer. Repeat extraction by again adding 3 ml of bathophenanthroline solution and 20 ml of alcohol with mixing. If no further extractions are indicated, make an extraction with alcohol alone and let settle a long enough time to remove all of the alcohol layer. Discard the alcohol layer. Iron, standard solution (1 ml =0.1 mg Fe). Dissolve 0. 1000 g of pure iron in 10 ml of HCl (1+1) and 12 ml of bromine water. Boil until excess bromine is removed. 33

vi)

vii)

Add 200 ml of HCI (1+1) cool and dilute to I litre in a volumetric flask with water. Iron, standard solution (1 ml=0.001 mg Fe) Pipette 10 ml of standard solution (1ml=0.1mg Fe) into a I litre flask, add 12 ml of HCl (1+1) and dilute to1 litre with iron-free water. Prepare the dilute solution fresh before use. viii) 17.5 Thioglycollic acid - reagent grade.

GLASS W ARE All glasswares must be cleaned in HCl before making an iron extraction. Drain and rinse with isoprophyl alcohol.

17.6

APPARATUS REQUIRED 500 ml polyethylene bottles with sample extraction hose. 250 ml separatory funnel 2 ml pipette (for conc. HCl) 2 ml pipette(for NH2 OH HCl) 2 ml pipette (for bathophenanthroline) 2 ml pipette (for thiogly collic acid) 25 ml pipette (for n-hexyl alcohol) 10 ml pipette (for iso-propyl alcohol) Spectrophotometer 5.0 cm cell - 0-5 ppb 2.0 cm cell - 50-200 ppb waterbath suitable for heating (thermostat)

17.7

APPLICATION RANGE OF APPARATUS Set spectrophotometer at 533 nm 5.0 cm cell 0-50 ppb 2.0 cm cell 50-200 ppb

17.8

PROCEDURE i) Place acidified sample bottle (with top off) in hot water bath for one hour after adding 2 ml of conc. HCl, 2ml of NH2 OH HCI, and 2 ml of thioglycollic acid (see Note). Cool to room temperature and transfer 200 ml of the samples to a 250 ml separatory funnel.

ii)

34

NOTE: The pH of a 500 ml feed water sample which has been acidified with 1 ml of concentrated HCl is approximately 1.5. At this low pH nearly all the iron oxide (Fe2 O3 +Fe3 O4 ) in the feed water will generally go into solution over a short period of time. However, the above digestion step in the water bath gives some assurance of complete solubility. Nevertheless an occasional sample will require prolonged heating and concentration. A magnet drawn across the bottom of the sample bottle that has been standing several hours will usually attract insoluble magnetite iii) Add 1ml of NH2 OH HCl and then 2 ml. of bathophenanthroline. (Shake for 30seconds). (Add 3 ml. for over 50 ppb Fe). Adjust pH with NH2 OH (1+1) or HCl (1+9) to pH 3.3 to 3.7. (This can be done with a single pH elecctrode hung down in the separatory funnel). Rinse electrode with distilled water before going to next sample. Add 25 ml. of n-hexyl alcohol and shake for 1 minute. Allow 5 minutes for separation and drain aqueous phase. Add 10ml. of isoprophyl alcohol to the funel and swirl to clear solution. Read colour.in the appropriate cell. NOTE: Isoamyl alcohol can also be used in place of Isopropyl alcohol.

iv)

V)

vi) vii)

18. DETERMINATION OF COPPER-NEOCUPROINE METHOD

18.1 INTRODUCTION This method covers the determination of total copper in the 2 to 2000 ppb range. This method is based upon the yellow colour produced by the neocuproine cuprous complex. A buffer solution maintains the pH between 4.0 to 6.0, but full colour development takes place over the range of 2.3 to 9.0. The hydroxylarnine hydrochloride reduces the copper to the cuprous state. 18.2 SAMPLING Although samples may be taken in polyethylene bottles, meticulously clean 500 ml glass bottles with plastic caps are preferred. Prepare bottles by soaking in HNO3 (1+9) for several hours prior to use. Then rinse bottles with distilled water and drain before sampling. Take the sample from the sample point, which has been continuously running for at least four hours. Do not overflow or rinse bottle. Do not touch valve or jar line.

35

18.3

STANDARDS Prepare a series of copper standards in 250 ml separatory funnels using the standard copper solution (1 ml =4 mg Cu). Add 1.0 ml of 1+1 HCL Dilute each to 200 ml include a blank and gtreat similarly. Application Range of Apparatus Set spectrophotometer at 454 nm 1.0 cm cell 20 to 1000 ppb. 10.0 cm cell 2 to 100 ppb.

18.4

REAGENTS i) Copper, Standard Solution (1 ml =0.02 mg Cu) weigh 0.200 g of electrolytic copper. Place it in a 250 ml beaker under a hood, add 3 ml of water and 3 ml of HNO3 (Sp.gr.1.42), and cover the beaker with a watch glass. After the metal hascompletely dissolved add 1ml of H2 SO4 (Sp.gr.1.84) and heat on a hot plate just short of complete dryness. Do not bake the residue. Cool the residue, wash down the sides of the beaker and the bottom of the watch glass, and again evaporate the solution nearly to dryness to expel the HN03- Cool the residue, dissolve it in water, and dilute the solution to 1 litre. Make the standard as needed by diluting 100ml. of the prepared solution to I litre with water. One millilitre of the standard contains 0.02 mg Cu or when diluted to 50 ml. with water it represents a 0.4 mg/litre (ppm) Cu solution. Copper, Standard Solution (1 ml = 4 mg Cu ) dilute 200 ml of copper solution (1ml=0.02 mg Cu) to I litre with water. One millilitre of this standard solution contains 4 mg of copper or, when diluted to 200 ml with water, it contains 20mg /litre(ppb). Concentrated hydrochloric acid (HCl). Hydroxylamine hydrochloride Solution (200 g/litre). Remove traces of copper from the solution prepared by treating in a separatory funnel with neocuproine solution and isoamyl Alcohol solvent in accordance with procedure. Discard the organic extract. Isoamyl Alcohol. Isopropyl Alcohol. Neocuproine solution (1g/litre)-Dissolve 0.1 9 of neocuproine (2,9 dimethy 1 -1, 10 - phenanthroline) in 50 ml. of isopropyl alcohol.Dilute the solution to 100 ml with water. Sodium acetate Solution (275 g/litre-Dissolve 55 g of sodium accetate trihydrate, (CH3 COONa 3H2 O) in water and dilute to 200 ml. Remove traces of copper from the solution by treating in a separatory funnel with NH2 OH. HCl, neocuproine, and isoamyl alcohol solvent solutions in accordance procedure. Discard the organic extract. 36

ii)

iii)

iv) v) vi)

vii)

* NOTE : Copper analysis should be run prior to iron. The copper in boiler feedwater is generally in the form of the soluble copper - ammonium complex and the acidified sample (approximately pH 1.5) will prevent plating out of elemental copper. The preliminary digestion step in the above procedure will generally assume complete solubility of low concentrations of copper (less than 50 ppb.) 18.5. APPARATUS REQUIRED 500 ml glass bottles with plastic caps with sample extraction hose. 250 ml - separating funnels 1 ml pipette (for 1:1 HCI) 1 ml pipette (for NH2 OH. HCl) 10 ml pipette (CH3 COONa solution) 2 ml and 4 ml pipettes (for neocuproine) 25 ml graduate (for isomyl alcohol) 10 ml graduate (for isoprophyl alcohol) Spectrophotometer 1.0 cm cell 20 to 1000 ppb 10.0 cm cell 2 to 100 ppb Waterbath suitable for heating (Thermostat).

18.6

PROCEDURE i) Place acidified sample bottle (with top off) in a hot water bath at 900o C for one hour (See Note) Cool to room temperature and transfer 200 ml of the sample to a 250ml separatory funnel. Add 1 ml of NH2 OH.HCl solution and mix by shaking. Add 10 ml of CH3 COONa solution and mix again. Then add 2 ml of neocuproine solution (4 ml for greater than 100g of Cu in sample). Mix by shaking. Allow to stand for about 3 min. Add 25 ml of isoamyl alcohol and shake for one minute. Allow to stand five minutes and permit aqueous phase to separate from alcohol phase. Alcohol phase will be at top and aqueous phase can be drained off. Collect alcohol layer and add 10 ml of isopropyl alcohol to clear solution. Swirl to mix thoroughly. Read in the appropriate cell at 454 nm.

ii)

iii) iv) V)

vi)

vii)

viii)

37

19. DETERMINATION OF AMMONIA

19.1 SUMMARY OF METHOD A sample aliquot is Nesslerised directly and ammonia content determined colorimetrically. Turbid samples may be clarified with ZnSO4 and NaOH. The precipitated Zn (OH)2 is filtered or centrifuged off and the ammonia is determined on clear aliquot by direct Nesslerization. 19.2 REAGENTS i) Ammonium Chloride - Standard Solution A Dissolve 3.819 g of anhydrous ammonium chloride NH4 Cl, dried at 105o C and diluted to 1000 ml. (1.0 ml.=1.00 mg N = 1.22 mg NH3 ). ii) Standard Solution B Take 10 ml of solution A and dilute to 1000 ml. (1.0 ml.= 10.0 mg N = 12.2 mg NH3 ) iii) Nessler Reagent Dissolve 100 g of anhydrous HgI2 and 70 g of anhydrous KI in a small volume of water, and add this mixture slowly, with stirring, to acooled solution of 160 g of NaOH in 500 ml of water. Dilute the mixture to1 litre. If this reagent is stored in a chemically resistant bottle out of direct sunlight, it will remain stable up to a period of 1 year. iv) Sodium Hydroxide Solution - 250 g per litre Dissolve 250 g of NaOH in water, and dilute to 1 litre. v) Sodium Potassium Tartrate Solution 500 g per litre Dissolve 500 g of sodium potassium tartrate tetrahydrate in 1 litre of water. Boil until ammonia-free, and dilute to 1litre. vi) Zinc Sulphate Solution (100 g per litre) Dissolve 100 g of ZnSO4 7 H2 O in water and dilute to 1litre. 19.3 APPARATUS REQUIRED Filter Stand with funnel, filter paper etc 1 ml, pipette (for ZnSO4 solution) 100 ml measuring cylinder 38

19.4

125 ml Erlemneyer flask 1 ml pipette (for Nessler reagent) Spectrophotometer Dropper - (for potassium sodium tartrate) PROCEDURE If the sample is turbid add ml ZnSO4 solution to 100 mi sample. Add NaOH until pH is 10.5.Filter and discard first 25 mi. (The above volume has not been changed appreciably). Dilute an aliquot portion to 50 mi in a 125 ml. Erlenmeyer. Add 2 drops of sodium potassium tartrate reagent and mix well. Then add 1 ml Nessler reagent. Allow 20 minutes for colour development and read on spectrophotometer at 460 nm. Use curve prepared but run atleast one standard with sample. Compare against reagent blank

20. DETERMINATION OF HYDRAZINE

20.1 SCOPE AND APPLICATION This method covers the colorimetric determination of hydrazine in industrial water. 20.2 SUMMARY OF METHOD Para - dimethylaminobenzalde hyde produces a specific yellow reaction product with hydrazine.The intensity of the yellow colour is proportional to the amount of hydrazine in the water. 20.3 INTERFERENCES i) The substances normally present in industrial water do not interfere with the test;however, the hydrazine content may be diminished by oxidizing agents collected with the sample or absorbed by it prior to testing. Colours in the prescribed wavelengths, also interfere as do other dark colours or turbidities that cannot be overcome by the prescribed treatment.

ii)

20.4

APPARATUS Colorimeter: A spectrophotometer suitable for measurements at 458 nm.

20.5

PURITY OF REAGENTS i) ii) Reagent grade chemicals shall be used in all tests. The purity of hydrazine di-hydrochloride may be established by iodimetric method making certain that all water used is oxygen-free & that all flasks and pipettes used are purged with nitrogen.Water for this reagent is best prepared by boiling and then cooling under a nitrogen blanket. 39

iii)

Para dimethylaminobenzaldehyde reagents obtained from different manufacturers produce different intensities of colour in solution. It is necessary that each new supply of reagent be tested on standard solutions before using with previously determined calibration curves.

20.6

REAGENTS i) Hydrazine, Standard Solution (1ml.= 0.1 mg N2 H4 ).Dissolve 0.328 g of hydrazine dihydrochloride (N2 H4 .2HCI). in 100 ml.of water and 10ml of HCl (Sp.gr.1.19). Dilute with water to 1litre in a volumetric flask, and mix. Hydrochloric Acid (Sp.gr. 1. 19) - Concentrated hydrochloric acid (HCl). Hydrochloric Acid (1:9) - Mix 1 volume of HCl (sp.gr. 1.19) with 9 volumes of water. Hydrochloric Acid (1:99) - Mix I volume of HCl (Sp.gr.1.19) with 99 volumes of water. Para-dimethylaminobenzaldehydesolution. Dissolve 4.0 g of p-dimethylaminobenzaldehyde in 200 ml. of methyl alcohol (CH3 OH) and 20 ml. of HCl (Sp.gr.1.19). Store in a dark bottle out of direct sunlight.

ii) iii)

iv)

v)

20.7

SAMPLING Analyse the sample as soon after collection as practicable, since hydrazine undergoes auto-oxidation as well as oxidising agents. Such agents may be in the sample or may enter the sample from the atmosphere. If it is suspected that oxidation of the hydrazine in the sample is occuring in the interval between collection and analysis, or if the sample is not to be analysed immediately, collect under acid. Place 5.0 ml. of HCl (1:9) in a 50 ml. volumetric flask, and collect sufficient sample in the flask, and bring the total volume to50 ml.

20.8

CALIBRATION i) Prepare a series of hydrazine standards by diluting measured volumes of the hydrazine solution (I mi. = 0.1 mg N2 H4 ) with HCl (1:99), so that a 50.0 ml.aliquid of each dilution will contain the desired quantity of hydrazine. Pipette 50.0 ml. portions of the hydrazine standards into 100 mi. beakers, flasks, or cylinders, and proceed as directed in procedure, except do not add more acid. Plot transmittance against micrograms of hydrazine (See Note).

ii)

Note :- A separate calibration curve must be made for each photometer and a recalibration must be made if it is necessary to change the cell, lamp or if any other alterations or instrument or reagents are made. Check the curve with each series of test : by running two or more solutions of known hydrazine concentrations. 40

20.9

PROCEDURE i) To a 100 mi. beaker, flask or cylinder, add from a burette exactly 5.0ml. or HCl (1:9) unless the sample was collected under acid, in which case proceed directly as described in paragraph (ii) except to use HCl (1:99) instead of water for diluting to 50.0 ml. By means of a graduated pipette, transfer to the 100 mi. beaker, flask or cylinder a portion of the sample that will contain approximately 0.20 to 5.0 pg of N2 H4 . Add water from a graduated burette or pipette to make a final volume of exactly 50 ml and mix. Add 10.0ml p-di-methylamino benzaldehyde solution with a pipette, and mix.Let the mixture stand atleast 10 min. and not more than 100 min. Measure and compare the colour by means of any of the apparatus listed. Make photometric measurements at approximately 458 nm. In photometric procedures, with water #showing no appreciable colour, prepare a blank containing no added hydrazine in order to correct for the colour of the unreacted p-dimethylaminobenzaldehyde and any optical effects involved in adjusting the photometer for 100 per cent transmission.

ii)

iii)

20.10

CALCULATION Calculate the hydrazine concentration in parts per million as follows: Hydrazine ppm = W/S Where W = micrograms of hydrazine found S = millilitres of sample.

21. DETERMINATION OF CHLORIDE (COLORIMETRIC METHOD)

21.1 APPLICATION This method may be applied to waters containing chloride ion in concentrations from 0.02 to 10 ppm. 21.2 SUMMARY OF METHOD Solutions of ferric, ammonium sulphate and mercuric thiocyanate are added to the sample.The chloride ion reacts with the mercuric thiocyanate to produce thiocyanate ion which in turn combines with ferric ion to form red ferric thiocyanate. The intensity of the colour which is proportional to the concentration of the chloride ion, is measured photometrically at a wave length of 463 nm.

41

21.3

INTERFERENCES Bromides, iodides, cynides, thiosulphates, and nitrites interfere in this method. Colour, if present in the sample, may interfere with the photometric measurement.

21.4 21.5

APPARATUS REQUIRED 50 ml - glass stoppered cylinder 25 ml - measuring cylinder 5 ml - pipette (for ferric ammonium solution) 5 ml - pipette (for mercuric thiocyanate solution) Spectrophotometer. REAGENTS i) Ferric alum solution Dissolve 5.0 g of ferrous ammonium sulphate (Fe(NH4 )2 (S04 )2 6H2 0) in 20 ml of water. Add 8 ml of concentrated nitric acid (HNO3 sp.gr. 1.42) and boil to oxidize the iron and remove the oxides of nitrogen. Dilute to 100 ml. with halidefree water. ii) Mercuric Thiocyanate, methanol Solution (3 g per litre) Dissolve 0.3 g of mercuric thiocyanate (Hg (CNS)2 in 100 ml of methanol. Store in amber bottles. Allow to stand for atleast 24 hours before using. (Caution: See below*). Do not use if more than four weeks old. *Caution :- Mercuric salts are very poisonous. Precautions should be observed when using this material. iii) Sodium Chloride, standard solution (10 mg Cl-per litre) Dry several grams of sodium chloride (NaCl) for I hour at 6000C. Prepare a stock solution by dissolving exactly 1.649g of the dry salt add water and dilute to 1 litre. Prepare standard solution as needed by diluting 10 ml of the stock solution to 1 litre with halid-free water. The resulting standard contains 10 mg of chloride ion per litre. Note: Soak all new glassware in hot nitric acid (HNO3 1:20) for several hours.

21.6

PROCEDURE i) Transfer 25 ml. of sample to a glass-stoppered cylinder and add successively 5 ml of ferric alum solution and 2.5 ml of mercuric thiocyanate solution. Mix thoroughly and allow to stand for 10 mts. Adjust the zero setting of the photometer (463 nm) by using 25 ml of halide-free water and treated as in step (i) under procedure. 42

ii)

iii) iv) 21.7

Measure the intensity of the colour using a spectrophotometer at 463nm. Read from the calibration graph.

CALIBRATION i) Prepare a series of standards by dilution suitable volumes of the standard chloride solution with halide-free water. Use 25 ml of halide-free water as blank. Treat the blank and the std. solutions as described in the procedure. ( 21.6 (i) ). Prepare a calibration graph by plotting the reading of the photometer versus the concentration of the chloride.

ii) iii) iv)

22. DETERMINATION OF MORPHOLINE

22.1 SCOPE AND APPLICATION i) This method covers the determination of morpholine in boiler feedwater and steam condensate. The method as described, may be applied to water containing morpholine in concentrations from I to 5 mg/litre (ppm). Higher concentrations may be determined by dilution.

ii)

22.2

SUMMARY OF METHOD i) The analysis for morpholine in water is based upon morpholines reaction to the sodium salt of 1,2- napthoquinone-4- sulfonic acid to form yellow coloured product with a minimum light transmittance at 480 nm. The intensity of the colour is determined spectrophotometrically and is directly proportional to the amount of morpholine in the sample in the range of 0 to 5 mg/litre.

22.3

SIGNIFICANCE i) Among its many applications, morpholine is used as a corrosion inhibitor in steamboiler systems. With its complete miscibility in water and its stability in hot liquid and gaseous phases at all temperatures, morpholine has the ability to maintain corrosion protection by neutralizing acid constituents such as carbonic acid, throughout the entire boiler systems.

43

In aqueous solution, morpholine ionizes as follows: O - (C 2 H4 )2 ---- NH+H2 O O --- (C 2 H4 )2 ---- NH2 OH O - (C 2 H4 )2 --- NH2 OH O --- (C 2 H4 )2 --- NH2 + OH

Thus through the addition of morpholine the pH of the system can be maintained in the 8.8 to 9.2 range of minimal carbon steel corrosion. Ammonia is muchmore volatile and is less effective in keeping all parts of the boiler system alkaline.Morpholine is generally injected into the feed train at a point following the condensate pump discharge. Examples of the pH of morpholine solutions is as follows: mg / litre pH 8.7 9.7 0.87 8.7

The vapors of morpholine are effective against external corrosion and tarnish caused by sulfur dioxide or hydrogen sulfide, but this application has received limited use. (ii) Morpholine (yetrahydro-1,4-oxazine)

is a colourless and hygroscopic liquid with a characteristic mild amine-like odour. It is a heterocyclic secondary amine which may also be described as an amino ether.The name came from the erroneous belief that it was related to morphine. It is completely miscible in water and miscible in a large number of organic solvents. Its density is slightly less than that of water at 200C and it has a boiling point of 128.90C.

22.4

INTERFERENCE This method is subject to interference from hydrazine, a chemical frequently used for oxygen scavenging i-i boiler systems.The interference can be eliminated by the addition of iodine solution, which oxidizes the hydrazine to nitrogen: N2 H4 + 41 - N2 +4HI If the samples are known to be without hydrazine, the full procedure should still be carried through if standardcurve exists in which the standards were treated with iodine. 44

22.5

APPARATUS Spectrophotometer, suitable for measurements between 450 and 5 10 nm. with 2.5cm cells. Water bath, suitable for maintaining a depth of approximately 4 cm, at a temperature of 550 to 650 C. Volumetric flasks - 100 ml. Graduated cylinder -100 ml. Burette Thermometer - range of 00 to 800 C Pipettes Accelerator scoops.

22.6

REAGENTS i) ii) iii) Purity of reagents-Reagent grade chemicals shall be used in all tests. Purity of water - D.M. Water Purified morpholine - 97% a) Standard solution 1 (1 ml =10 mg. 10,000 mg/litre) pipette 10.0 ml of approximately 100% morpholine into a I -litre volumetric flask and dilute to volume with water. Standard solution 11 (1 ml=1 mg, 1000 mg/litre) pipette 10.0 ml of standard solution1I into a 100 ml volumetric flask and dilute to volume with water.

b)

iv) V) vi)

Iodine solution - 0.0250 N Sodium bi-carbonate (NaHC03) - Reagent grade. Indicator solution - Sodium salt of 1,2 napthoquinone 4 -sulfonic acid -0.3 gm dissolved in 10 ml. of water. This solution must be prepared fresh every 24 hours, when needed. Stabilized starch powder - Thyodene.

vii) 22.7

SAFETY PRECAUTIONS i) Morpholines greates t laboratory hazard is that it penetrates the skin readily. If clothing or parts of the body become contaminated, the affected garments should be removed and the affected areas should be washed thoroughly with soap and water.Morpholine is not particularly toxic but serious effects are to be expected if appreciable quantities are taken internally. Vapour concentrations likely to develope under ordinary working conditions constitute little immediate hazard to health. Glassware used during analysis, should be rinsed with 1:1 HCI, followed by several rinses with water in order to remove the film residue left by morpholine. 45

ii)

22.8

CALIBRATION AND STANDARDIZATION i) Prepare a series of morpholine standards by diluting 1.0,2.0,3.0,4.0, and 5.0 ml. of the morpholine standard solution 11 (Sec 22.6.iii) each to I litre with water. These standards contain 1,2,3,4 and 5 mg/litre, respectively. Treat 50.0 ml. of each reference standard and a blank in accordance with section 22.9 (i to vii) Set up the spectrophotometer in the absorbance mode according to the procedure outlined in the manufacturers instruction manual for a wavelength of 480 nm with an appropriate slit width. Use the blank to zero the instrument and record the absorbance readings of the standards. Prepare a calibration curve by plotting the absorbance versus the concentration of linear graph paper. The curve should be linear and is considered acceptable if within + 0.5 ppm of the previous graph. On subsequent analysis, one standard should be run with the samples in order to setup the instrument and to verify the curve. The standard chosen should approximate the expected value of rrorpholine in the samples. According to the quality assurance programme, a new set of standards should be prepared when two-thirds of the volume of the existing set has been used.

ii)

iii)

iv)

v)

22.9

PROCEDURE i) For samples with concentrations expected to fall within the 0-5 mg/litre range measure 50.0 ml into a 100 ml volumetric flask.For samples with higher concentrations,prepare dilutions, record the dilution, factors and proceed as in 10. 1 Add one scoop of sodium bicarbonate (NaHCO3 ) Add one scoop of stabilizer starch powder (Thyodene) to each flask. Stopper and mix. With swirling, titrate the contents of each flask with iodine solution to the permanent blue end point. Transfer the contents of each flask to a graduate, dilute to 60 ml. and return to its flask. Add 0.2 ml.(4 drops) indicator solution to each flask. Swirl. Place the flasks into the water bath which is at 55-650C. Loosen stoppers and with a thermometer in the blank, heat the samples to 40-430C. Remove from bath and let them stand for 3 - 4 minutes. Zero the spectrophotometer at 480 nm with the blank using the 2 cm cells. Read the chosen standard. Read the absorbance of samples on spectrophotometers. 46

ii) iii)

iv)

v)

vi) vii)

viii)

22.11

CALCULATIONS i) ii) Absorbance values are converted directly to mg/litre from the standard curve. Apply dilution factors, if any.

23. DETERMINATION OF CYCLOHEXYLAMINE

23.1 SCOPE AND APPLICATION This method covers a colorimetric procedure for the determination of cyclohexylarnine in boiler feed water and steam condensate. The method, as described, may be applied to waters containing cyclohexylamine in concentrations from 0.25 to 10 mg/litre. Higher concentrations may be determined by sample dilution. 23.2 SUMMARY OF METHOD The method is based on the diazotization of p-nitro-aniline with sodium nitrate in the presence of hydrochloric acid and the subsequent coupling of the diazoniurn chloride formed with cyclohexylamine to produce a strongly coloured reddish compound. The red compound is extracted with isoamyl alcohol for concentration and reduction of background colour. The colour of the extract is measured photometrically after treatment with an alcoholic solution of sodium hydroxide. 23.3 INTERFERENCES None of the constituents present in the usual feed water causes difficulty in the method. As much as I to 2 mg/litre of iron can be tolerated. Morpholine does not interefere.Ammonia produces a reaction similar to cyclohexylamine: however at 530 nm at which the colour is measured, 6 to 7 mg/litre of NH3 is required to produce the same absorbance as I mg/litre of cyclohexylamine. Less ammonia can be tolerated if the colour is measured at a wavelength lower than 530 nm. One mg/litre of hydrazine produces a positive error in the test equivalent to 0.5 mg / litre of cyclohexylamine.Neither triethanolamine nor triethylamine interfere, but monoethanolamine is measured in the test. 23.4 APPARATUS Filter photometer or spectrophotometer, suitable for measurements at a wavelength of 530 nm.

47

23.5

REAGENTS i) Purity of reagents Reagent grade chemicals shall be used in all tests. ii) Purity of water DM water iii) Buffer solution Dissolve 50 g of potassium hydroxide (KOH) and 70 g of boric acid (H3 BO3 ) in about 700 ml of water. Dilute solution to 1 litre with water. iv) Cyclohexylamine, standard solution (1 ml = 0.1 mg) CYCLOHEXYLAMINE: Prepare a stock solution by weighing 1.00 g of technical cyclohexylamine ( purity over 99%) in a weighing bottle, transferring the material to about 800 mi of water,and diluting the solution to 1 litre. Prepare the standard solution by diluting 100 ml of the stock solution to 1 litre with water. V) vi) vii) Isoamyl alcohol Methyl alcohol Nitroaniline solution (10 g/litre) Dissolve 1g of p-nitroaniline (Eastman No. 179 or equivalent) in a mixture of 25 ml of hydrochloric acid (sp.gr 1.19) and 75 ml of water. viii) Sodium hydroxide solution (80 g/litre) Dissolve 20 g of sodium hydroxide (NaOH) in 200 ml of water. Cool and dilute solution to 250ml with water. ix) Sodium hydroxide alcoholic Solution (20 g/litre) Dissolve 20 g of sodium hydroxide (NaOH) in 150 mi. of water. Add the solution to 800ml methyl alcohol and dilute to 1 litre with water. x) Sodium Nitrite Solution Dissolve 0.575 g of sodium nitrite (NaN02) in water and dilute solution to 100 ml with water.Prepare solution fresh atleast once every two weeks. 48

23.6 i)

PHOTOMETER CALIBRATION Prepare a series of cyclohexylarnine standards to contain 0-10mg/litre by diluting 0 to 10 ml of cyclohexylarnine standard solution to 100 ml with water. Develope colour in the series of standards as directed in procedure. Measure the absorbance of alcoholic extract obtained from each std. in a 10 mm or 20 mm cell at 530 nm with a photometer. For the initial photometer setting to zero, use methyl alcohol as the reference solution. Plot absorbance versus mg/litre of cydlohexylamine on linear graph paper . A line that deviates only slightly from being straight should be obtained.

ii)

iii)

23.7

PROCEDURE i) Pipette into a clean 250 ml separatory funnel, 1 ml of nitroaniline solution and 1 ml of NaNO2 solution (Caution, see Note 1). Immediately cap and swirl the funnel to mix contents. Between 2 & 3 minute after the mixing step (Note 2), add 100 ml of the sample, if necessary, cooled to room temperature. Cap the funnel and shake to mix the contents. Note 1: Caution : Use a safety pipette or burette to measure the nitroaniline solution. Note 2: Slightly lower cyclohexylamine values are obtained if a time interval longer than 3 minutes is allowed for the diazotization step. ii) Immediately add 10 ml of buffer solution, cap the funnel and shake several times to mix contents (Note 3). Start a stop watch as soon as possible after mixing. At the end of 30th seconds (Note 4) add 4 ml of NaOH solution by means of a 10 ml graduated cylinder and mix the contents immediately.

Note 3: The solution should have a pH of 9.0 0.2 after the addition of the buffer solution.Low results will be obtained at pH values below this level. Note 4: Time allowed for coupling is critical and stop watch accuracy in timing is needed. As much as 25% more colour is formed if 60s are allowed for coupling. Colour fades appreciably after 60s.

iii)

Add 10 ml of isoamyl alcohol by means of a graduated cylinder to the funnel. Invert funnel atleast 20 times to extract the reddish-coloured compound into the alcohol. Avoid vigorousshaking since an emulsion can result. Permit the funnel to stand for about 5 minutes to allow the two layers to separate. Transfer the bottom aqueous layer into a clean separatory funnel. Retain the alcoholic layer in the original funnel. Make a second extraction of the aqueous layer by repeating step 3 (previous step) with an additional 10 ml of isoamyl alcohol. 49

iv)

Discard the aqueous layer and add the alcoholic layer from the second extraction to the original funnel containing the first extract. Mix the two extracts by swirling the funnel and allow any water droplets to settle. V) Pipette 5 ml of the alcoholic extract into a dry, Erlenmeyer flask (Caution, See Note 1) add 45 ml of alcoholic caustic solution to the flask with a graduated cylinder. Mix the contents by swirling the flask. Measure the absorbance of the red-coloured solution with a photometer, using methyl alcohol as the reference solution for the initial photometer setting.

vi)

23.8

CALCULATION Calculate the concentration of cyclohexylamine in milligrams per litre as follows: Cyclohexylamine, mg/litre (ppm) =W x (100/S) where W S = mg/litre of cyclohexylamine indicated by the calibration curve = millilitres of sample used.

24.

DETERMINATION OF SODIUM (FLAME PHOTOMETER)

24.1 INTRODUCTION When a solution containing dissolved sodium is aspirated into a flame, a characteristic yellow-orange colour results. The intensity of this flame is a function of concentration.The flame filter photometer is the apparatus used for measuring the intensity of this emitted light. 24.2 APPARATUS REQUIRED i) ii) iii) iv) V) vi) vii) 24.3 Filter flame photometer with compressor Indane gas with regulator Gas ignitor Polythene tubes for gas and air Filter for sodium 5 c.c. beakers A spot galvanometer.

REAGENTS Standard sodium solution Dissolve 2.542 gms of analar grade sodium chloride in one litre of sodium free water in a volumetric flask. This solution contains 1.000 mg of sodium per one ml. or this can be diluted for the required standard solution and stored in polythene bottles as glass bottle will contaminate the solution. 50

24.4

PROCEDURE i) Boiler Water Standardisation of filter flame photometer Air supply for the burner is to be provided from the air compressor which should deliver dry oil free air at a pressure of 1 kg/cm2 a) b) c) d) e) f) g) h) i) Connect the instrument to power supply. Connect the compressor and the gas ignitor to the sockets in the cabinet. Turn the sensitivity control fully anti-clockwise Insert the sodium filter Switch on mains and wait for five minutes so that the amplifier is stabilised. Bring the pointer of the meter to zero by adjusting set zero Open the air control and adjust the pressure of air to 0.7 kg/cm Turn the gas control and light the burner with the ignitor Slowly turn the gas control till the blue flame is obtained. At the start the flame may be noisy and wait for five minutes. Feed sodium free distilled water through the atomiser. This is done by dipping the PVC capillary tube into a beaker of distilled water. Adjust zero Aspirate 2 ppm standard sodium solution and adjust the needle of the meter to 100 with the sensitivity control. Repeat steps 10,11 and 12 to ascertain the repeatability. This should be checked from time to time in a series of tests. Introduce. the boiler water into a 5 c.c. beaker and aspirate the same. From the meter reading calculate sodium concentration in ppm. If the meter reading exceeds 100, (or the maximum reading) suitably dilut the boiler water with sodium free water.

j)

k) l)

m)

n) o) p)

51

ii)

Saturated steam, superheated steam, condensate, feed water. a) Repeat steps a to k (setting up of the instruments after connecting the spot galvanometer to the main instrument).Check that the spot galvanometer is in line. Aspirate 0.1 ppm standard sodium solution and adjust the spot to100 with the sensitivity control. Repeat steps j,k and l to ascertain the repeatability. This should be checked from time to time in a series of tests. Introduce condensed saturated steam or superheated steam or condensate or feed water (as the case may be) into a 5 ml. beaker and aspirate the same. From the spot reading, calculate sodium concentration in ppm.

b)

c)

d)

e) 24.5

GENERAL The instrument should be located in an area away from direct sun light, and be free of draft, dust and tobacco fumes (when low levels of sodium is being determined) . Precautions should be enforced against contamination originating from perspiration, soap, cleanser, cleaning mixtures and inadequately rinsed apparatus.

25. DETERMINATION OF SODIUM- LOW LEVEL (Online Method)

25.1 INTRODUCTION On-line sodium detector is used for continuously measuring very low levels of sodium (0.1 to 1000 ppb) in dernineralisation outputs, feed water, steam and condensate samples. The sample stream passes through the sample valve, a filter, a pressure regulator and a flow meter. The sample then passes through a reagent diffusion bottle where pH adjustment takes place, and then flows to the electrode holder assembly, containing the sodium and reference electrodes. The instrument has a thermistor which automatically compensates for changes in sample temperature.

25.2

APPARATUS i) ii) iii) On-line sodium measuring instrument Dynamic Calibrator Printer (Optional)

52

25.3

REAGENTS i) Sodium standardising solution(10 ppm Na and 1 ppm, Na).

25.4

PROCEDURE i) Sample requirement A sample line with 1/8 inch MNPT connector and a shut-off valve must be delivered to th e inlet connector of the instrument, at a flow rate between 50ml/min. and 2litres/min. The temperature of the sample at the sample inlet point must be below 45o C. Steam must not be allowed to enter the instrument. The sample must be delivered between 20 and 100 psig pressure and the pH should not be below 6. ii) Calibration a) The main instrument is permanently bolted in an upright position and necessary power connections are given. The sodium and reference electrodes are handled carefully. The sodium electrode is treated with the conditioning solution and rinsed with deionized water before use. The proper calibrating range (eg. 10 to 100 ppb for steam samples) is selected. The calibration procedure given by the manufacturer is strictly followed. The instrument is calibrated once in every month for reliable results.

b)

C) d)

iii)

Measurement After the calibration, the instrument is put on stream for continuous measurement.

53

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PRESERVATION OF BOILERS

PUB.NO. 2004

CONTENTS
INTRODUCTION WET LAY-UP FIG.1 SCHEME FOR NITROGEN BLANKETTING FIG.2 SCHEME FOR HYDRAULIC PRESSURE TABLE-I RECOMMENDED LAY-UP PROCEDURES (Drum Type Units)

INTRODUCTION Atmospheric corrosion of ferritic materials proceeds rapidly in the presence of oxygen and moisture.The oxides produced are objectionable and can be transported to critical heat transfer areas as well as to the turbine. Also, through the wall, pit type corrosion can occur. In todays large boilers with their numerous complex circuits and bends, it is usually impossible to completely dry a boiler in preparation for storage. Draining all circuits (if drainable) while hot may temporarily dry the surfaces; howe ver, unless dry air can be continuously circulated to eliminate all the water vapour from the unit, recondensation will again result in moist conditions. For this reason,wet lay-up normally offers the most positive method of protection for components in modern boilers. Modern high-pressuie systems also require protection of auxiliary equipment like feed water system components. WET LAY-UP The wet lay-up method employs the principle of filling up the system with water treated with ammonia and hydrazine and applying a positive nitrogen pressure of about 0.35 atg. in order to prevent air in leakage. Alternately, an hydraulic pressure of about 5 atg. can be maintained to prevent air in leakage. Condensate or dernineralised water should only be used for all non-drainable sections. Complete lay-up recommendations are given in Table-1. Figure 1 indicates the general arrangement of the rig up required for Nitrogen blanketing. A bank of Nitrogen cylinders can be employed for the purpose. The Nitrogen supply can be connected to the drum vent and superheater outlet header drain/vent. If hydraulic pressure is desired in the place of Nitrogen blanketing, it is recommended to rig up an.open storage tank of 5 to 10 tonnes capacity where demineralised water can be taken and the required chemicals added. From this, a pump can be installed to feed the boiler. The pump can be of 10 to 25 tonnes/hr. capacity with a head of 7 to 10 atm. Smaller the pump, longer it will take for filling the boiler. The same pump can be used to develop a prcssure of 5 atm after filling the boiler. The same pump can be used to develop a pressure of 5 atm after filling the boiler. The same pump can be run everyday for a few hours to maintain the pressure. A return line from the boiler to the tank can be arranged so that the chemicals can be replenished. The schematic is shown in Figure-2.

FIG.1 SCHEME FOR NITROGEN BLANKETTING

FIG.2 SCHEME FOR HYDRAULIC PRESSURE

TABLE - 1 RECOMMENDED LAY-UP PROCEDURES (Drum Type Units)

Type of Shut Down Pre - operational period post hydro (see Note-1) Procedure With the boiler filled to overflowing pressurize the unit with nitrogen to 0.35 itg. pressure (see notes 5 & 6) 1.Introduce condensate con taining 10 PPM ofammonia and 200 PPM of hydrazine into the superheater feed water heaters (tube side) and associated piping, economiser and boiler (Refer to note 3). Notes 1. All non-drainable sections to be hydrostatically tested should be filled with condensate or demineralized water containing 10 PPM of ammonia and 200 PPM of ammonia and 200 PPM of hydrazine. This should produce a solution pH of approximately 10. The superheater should be filled first to overflow into the boiler drum. Then the boiler can be filled through normal fill connections (see note 2) with demineralized or if not available any source of clean, filtered water.

Pre-operational period post chemical cleaning (effective for four weeks only)

2. Nitrogen cap the superheater, feed water heater (shell side) and drum. Maintain 0.35 atg. nitrogen pressure (see notes 4&5). Short outage 4 days or less unit not drained 1. Maintain the same hydrazine and ammonia concentrations as those present during normal operation and normal water level in boiler. 2. Establish and maintain 0.35 aig. nitrogen cap on the superheater and the steam drum (see notes 4 & 5). 3. Nitrogen cap the shell side of the feedwater heaters. Short outage 4 days or less unit drained. 1. Drain and open only those sections requiring repairs. 2. Isolate remainder of unit under 0.35 atg nitrogen pressure where possible (see notes 4&5). 3. Maintain the same hydrazine and ammonia concentration for water remaining in the cycle as those present during normal operation. 4. Nitrogen cap the shell side of the feedwater heaters.

2. Hydrazine and ammonia may be added to the system in two ways. a) By pumping concentrated solutions through the chemical feed equipment. b) Condenser leakage is not a cause for shut-down, concentrated solutions can be introduced directly into the hotwell. If condensate demineralization is employed, it must be bypassed during this operation.

It is important to have fluid temperature in the cycle below 200 0C before addition of hydrazine. If this temperature is exceeded the hydrazine will decompose.

3. The tube side of copper alloy feedwater heaters should be filled with de-mineralized water containing 0.5 PPM of ammonia and 50 PPM of hydrazine.

Type of Shut Down

Procedure

Notes

Long outage longer than 4 days Unit not drained.

1.Fill the superheater and re-heater with condensate containing 10 PPM of ammonia and 2W PPM of hydrazine. The pH of the solution should be approximately 10.0. Add t he condensate from the outlet of the non drainable sections.

4. If the reheater can be isolated, it can also he capped with 0.35 atg nitrogen. When the outage is expected to extend beyond 2 months provisions should be made to isolate and nitrogen cap the reheater if this was not done previously. 5. Nitrogen cap sh ould be applied through the drum vent & superheater outlet header drain/vent as the unit is cooled. When pressure drops to 0.35 atg. Admission of air through atmospheric vents should be avoided. 6. If freezing is a problem, the water in drainable circuits can be displaced with nitrogen and the unit layed up under 0.35atg. nitrogen pressure Auxiliary heat may he applied to keep the non -drainable secimns from freezing. General Note:During every cold start, visually check the feedwater. If it is dirty, drain to waste from heater drips and deaerator tank. Clear water should only be admitted into the boiler and used for desuperheater spray from the beginning.

2. Increase the hydrazine &ammonia concentrations in the boiler,. economiser and feedwater heaters (tube side) and associated piping to 200PPM and 10 PPM respectively (see notes 2,3 and 6).

3. Establish and maintain a 0.35atg. nitrogen cap on the superheater and steam drum (see notes 4 & 5).

4. Nitrogen cap the shell side of the feedwater heaters. Long outage longer than 4 days unit drained. 1. Drain and open only those sections requiring repairs. 2. Fill the superheater and re heater (if not requ iring draining for repairs) with Condensate containing 10PPM of ammonia and 200 PPM of hydrazine.The pH of the solution should be approximately 10,0. Add the condensate from the outlet of the non drainable sections.

3. Increase the hydrazine and ammonia concentrations in the tube side of the feedwater heaters and the undrained circuits in the boiler to 200 PPM and 10 PPM respectively. (See notes 2 & 3)

4. Establish and maintain 0.35 atg nitrogen cap on the un-drained sectioin of the un it where possible. (See Notes 4&5) 5. Nitrogen cap the shell side of the feedwater headers. 6. After completion of the repairs fill the drained sections with condensate (dernineralized water containing 10 PPM of ammonia and 200 PPM of hydrazine. Cap with nitrogen. (See Notes 2, 3 & 6).

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