Chapter 9

Chapter 93,343 wordsPublic domain

Water has a greater specific heat or heat-absorbing capacity than any other known substance (bromine and hydrogen excepted) and its specific heat is the basis for measurement of the capacity of heat absorption of all other substances. From the definition, the specific heat of water is the number of British thermal units required to raise one pound of water one degree. This specific heat varies with the temperature of the water. The generally accepted values are given in Table 13, which indicates the values as determined by Messrs. Marks and Davis and Mr. Peabody.

TABLE 13

SPECIFIC HEAT OF WATER AT VARIOUS TEMPERATURES

+----------------------+--------------------------------+ | MARKS AND DAVIS | PEABODY | | From Values of | From Values of | | Barnes and Dieterici | Barnes and Regnault | +-----------+----------+---------------------+----------+ |Temperature| Specific | Temperature | Specific | +-----------+ Heat +----------+----------+ Heat | | Degrees | | Degrees | Degrees | | |Fahrenheit | |Centigrade|Fahrenheit| | +-----------+----------+----------+----------+----------+ | 30 | 1.0098 | 0 | 32 | 1.0094 | | 40 | 1.0045 | 5 | 41 | 1.0053 | | 50 | 1.0012 | 10 | 50 | 1.0023 | | 55 | 1.0000 | 15 | 59 | 1.0003 | | 60 | 0.9990 | 16.11 | 61 | 1.0000 | | 70 | 0.9977 | 20 | 68 | 0.9990 | | 80 | 0.9970 | 25 | 77 | 0.9981 | | 90 | 0.9967 | 30 | 86 | 0.9976 | | 100 | 0.9967 | 35 | 95 | 0.9974 | | 110 | 0.9970 | 40 | 104 | 0.9974 | | 120 | 0.9974 | 45 | 113 | 0.9976 | | 130 | 0.9979 | 50 | 122 | 0.9980 | | 140 | 0.9986 | 55 | 131 | 0.9985 | | 150 | 0.9994 | 60 | 140 | 0.9994 | | 160 | 1.0002 | 65 | 149 | 1.0004 | | 170 | 1.0010 | 70 | 158 | 1.0015 | | 180 | 1.0019 | 75 | 167 | 1.0028 | | 190 | 1.0029 | 80 | 176 | 1.0042 | | 200 | 1.0039 | 85 | 185 | 1.0056 | | 210 | 1.0052 | 90 | 194 | 1.0071 | | 220 | 1.007 | 95 | 203 | 1.0086 | | 230 | 1.009 | 100 | 212 | 1.0101 | +-----------+----------+----------+----------+----------+

In consequence of this variation in specific heat, the variation in the heat of the liquid of the water at different temperatures is not a constant. Table 22[13] gives the heat of the liquid in a pound of water at temperatures ranging from 32 to 340 degrees Fahrenheit.

The specific heat of ice at 32 degrees is 0.463. The specific heat of saturated steam (ice and saturated steam representing the other forms in which water may exist), is something that is difficult to define in any way which will not be misleading. When no liquid is present the specific heat of saturated steam is negative.[14] The use of the value of the specific heat of steam is practically limited to instances where superheat is present, and the specific heat of superheated steam is covered later in the book.

BOILER FEED WATER

All natural waters contain some impurities which, when introduced into a boiler, may appear as solids. In view of the apparent present-day tendency toward large size boiler units and high overloads, the importance of the use of pure water for boiler feed purposes cannot be over-estimated.

Ordinarily, when water of sufficient purity for such use is not at hand, the supply available may be rendered suitable by some process of treatment. Against the cost of such treatment, there are many factors to be considered. With water in which there is a marked tendency toward scale formation, the interest and depreciation on the added boiler units necessary to allow for the systematic cleaning of certain units must be taken into consideration. Again there is a considerable loss in taking boilers off for cleaning and replacing them on the line. On the other hand, the decrease in capacity and efficiency accompanying an increased incrustation of boilers in use has been too generally discussed to need repetition here. Many experiments have been made and actual figures reported as to this decrease, but in general, such figures apply only to the particular set of conditions found in the plant where the boiler in question was tested. So many factors enter into the effect of scale on capacity and economy that it is impossible to give any accurate figures on such decrease that will serve all cases, but that it is large has been thoroughly proven.

While it is almost invariably true that practically any cost of treatment will pay a return on the investment of the apparatus, the fact must not be overlooked that there are certain waters which should never be used for boiler feed purposes and which no treatment can render suitable for such purpose. In such cases, the only remedy is the securing of other feed supply or the employment of evaporators for distilling the feed water as in marine service.

TABLE 14

APPROXIMATE CLASSIFICATION OF IMPURITIES FOUND IN FEED WATERS THEIR EFFECT AND ORDINARY METHODS OF RELIEF

It is evident that the whole subject of boiler feed waters and their treatment is one for the chemist rather than for the engineer. A brief outline of the difficulties that may be experienced from the use of poor feed water and a suggestion as to a method of overcoming certain of these difficulties is all that will be attempted here. Such a brief outline of the subject, however, will indicate the necessity for a chemical analysis of any water before a treatment is tried and the necessity of adapting the treatment in each case to the nature of the difficulties that may be experienced.

Table 14 gives a list of impurities which may be found in boiler feed water, grouped according to their effect on boiler operation and giving the customary method used for overcoming difficulty to which they lead.

Scale--Scale is formed on boiler heating surfaces by the depositing of impurities in the feed water in the form of a more or less hard adherent crust. Such deposits are due to the fact that water loses its soluble power at high temperatures or because the concentration becomes so high, due to evaporation, that the impurities crystallize and adhere to the boiler surfaces. The opportunity for formation of scale in a boiler will be apparent when it is realized that during a month's operation of a 100 horse-power boiler, 300 pounds of solid matter may be deposited from water containing only 7 grains per gallon, while some spring and well waters contain sufficient to cause a deposit of as high as 2000 pounds.

The salts usually responsible for such incrustation are the carbonates and sulphates of lime and magnesia, and boiler feed treatment in general deals with the getting rid of these salts more or less completely.

TABLE 15

SOLUBILITY OF MINERAL SALTS IN WATER (SPARKS) IN GRAINS PER U. S. GALLON (58,381 GRAINS), EXCEPT AS NOTED

CALCIUM SULPHATE AT TEMPERATURE ABOVE 212 DEGREES (CHRISTIE)

+------------------------------+----+----+-------+----+---+ |Temperature degrees Fahrenheit|284 |329 |347-365| 464|482| |Corresponding gauge pressure | 38 | 87 |115-149| 469|561| |Grains per gallon |45.5|32.7| 15.7 |10.5|9.3| +------------------------------+----+----+-------+----+---+

Table 15 gives the solubility of these mineral salts in water at various temperatures in grains per U. S. gallon (58,381 grains). It will be seen from this table that the carbonates of lime and magnesium are not soluble above 212 degrees, and calcium sulphate while somewhat insoluble above 212 degrees becomes more greatly so as the temperature increases.

Scale is also formed by the settling of mud and sediment carried in suspension in water. This may bake or be cemented to a hard scale when mixed with other scale-forming ingredients.

Corrosion--Corrosion, or a chemical action leading to the actual destruction of the boiler metal, is due to the solvent or oxidizing properties of the feed water. It results from the presence of acid, either free or developed[15] in the feed, the admixture of air with the feed water, or as a result of a galvanic action. In boilers it takes several forms:

1st. Pitting, which consists of isolated spots of active corrosion which does not attack the boiler as a whole.

2nd. General corrosion, produced by naturally acid waters and where the amount is so even and continuous that no accurate estimate of the metal eaten away may be made.

3rd. Grooving, which, while largely a mechanical action which may occur in neutral waters, is intensified by acidity.

Foaming--This phenomenon, which ordinarily occurs with waters contaminated with sewage or organic growths, is due to the fact that the suspended particles collect on the surface of the water in the boiler and render difficult the liberation of steam bubbles arising to that surface. It sometimes occurs with water containing carbonates in solution in which a light flocculent precipitate will be formed on the surface of the water. Again, it is the result of an excess of sodium carbonate used in treatment for some other difficulty where animal or vegetable oil finds its way into the boiler.

Priming--Priming, or the passing off of steam from a boiler in belches, is caused by the concentration of sodium carbonate, sodium sulphate or sodium chloride in solution. Sodium sulphate is found in many southern waters and also where calcium or magnesium sulphate is precipitated with soda ash.

Treatment of Feed Water--For scale formation. The treatment of feed water, carrying scale-forming ingredients, is along two main lines: 1st, by chemical means by which such impurities as are carried by the water are caused to precipitate; and 2nd, by the means of heat, which results in the reduction of the power of water to hold certain salts in solution. The latter method alone is sufficient in the case of certain temporarily hard waters, but the heat treatment, in general, is used in connection with a chemical treatment to assist the latter.

Before going further into detail as to the treatment of water, it may be well to define certain terms used.

_Hardness_, which is the most widely known evidence of the presence in water of scale-forming matter, is that quality, the variation of which makes it more difficult to obtain a lather or suds from soap in one water than in another. This action is made use of in the soap test for hardness described later. Hardness is ordinarily classed as either temporary or permanent. Temporarily hard waters are those containing carbonates of lime and magnesium, which may be precipitated by boiling at 212 degrees and which, if they contain no other scale-forming ingredients, become "soft" under such treatment. Permanently hard waters are those containing mainly calcium sulphate, which is only precipitated at the high temperatures found in the boiler itself, 300 degrees Fahrenheit or more. The scale of hardness is an arbitrary one, based on the number of grains of solids per gallon and waters may be classed on such a basis as follows: 1-10 grain per gallon, soft water; 10-20 grain per gallon, moderately hard water; above 25 grains per gallon, very hard water.

_Alkalinity_ is a general term used for waters containing compounds with the power of neutralizing acids.

_Causticity_, as used in water treatment, is a term coined by A. McGill, indicating the presence of an excess of lime added during treatment. Though such presence would also indicate alkalinity, the term is arbitrarily used to apply to those hydrates whose presence is indicated by phenolphthalein.

Of the chemical methods of water treatment, there are three general processes:

1st. Lime Process. The lime process is used for waters containing bicarbonates of lime and magnesia. Slacked lime in solution, as lime water, is the reagent used. This combines with the carbonic acid which is present, either free or as carbonates, to form an insoluble monocarbonate of lime. The soluble bicarbonates of lime and magnesia, losing their carbonic acid, thereby become insoluble and precipitate.

2nd. Soda Process. The soda process is used for waters containing sulphates of lime and magnesia. Carbonate of soda and hydrate of soda (caustic soda) are used either alone or together as the reagents. Carbonate of soda, added to water containing little or no carbonic acid or bicarbonates, decomposes the sulphates to form insoluble carbonate of lime or magnesia which precipitate, the neutral soda remaining in solution. If free carbonic acid or bicarbonates are present, bicarbonate of lime is formed and remains in solution, though under the action of heat, the carbon dioxide will be driven off and insoluble monocarbonates will be formed. Caustic soda used in this process causes a more energetic action, it being presumed that the caustic soda absorbs the carbonic acid, becomes carbonate of soda and acts as above.

3rd. Lime and Soda Process. This process, which is the combination of the first two, is by far the most generally used in water purification. Such a method is used where sulphates of lime and magnesia are contained in the water, together with such quantity of carbonic acid or bicarbonates as to impair the action of the soda. Sufficient soda is used to break down the sulphates of lime and magnesia and as much lime added as is required to absorb the carbonic acid not taken up in the soda reaction.

All of the apparatus for effecting such treatment of feed waters is approximately the same in its chemical action, the numerous systems differing in the methods of introduction and handling of the reagents.

The methods of testing water treated by an apparatus of this description follow.

When properly treated, alkalinity, hardness and causticity should be in the approximate relation of 6, 5 and 4. When too much lime is used in the treatment, the causticity in the purified water, as indicated by the acid test, will be nearly equal to the alkalinity. If too little lime is used, the causticity will fall to approximately half the alkalinity. The hardness should not be in excess of two points less than the alkalinity. Where too great a quantity of soda is used, the hardness is lowered and the alkalinity raised. If too little soda, the hardness is raised and the alkalinity lowered.

Alkalinity and causticity are tested with a standard solution of sulphuric acid. A standard soap solution is used for testing for hardness and a silver nitrate solution may also be used for determining whether an excess of lime has been used in the treatment.

Alkalinity: To 50 cubic centimeters of treated water, to which there has been added sufficient methylorange to color it, add the acid solution, drop by drop, until the mixture is on the point of turning red. As the acid solution is first added, the red color, which shows quickly, disappears on shaking the mixture, and this color disappears more slowly as the critical point is approached. One-tenth cubic centimeter of the standard acid solution corresponds to one degree of alkalinity.

Causticity: To 50 cubic centimeters of treated water, to which there has been added one drop of phenolphthalein dissolved in alcohol to give the water a pinkish color, add the acid solution, drop by drop, shaking after each addition, until the color entirely disappears. One-tenth cubic centimeter of acid solution corresponds to one degree of causticity.

The alkalinity may be determined from the same sample tested for causticity by the coloring with methylorange and adding the acid until the sample is on the point of turning red. The total acid added in determining both causticity and alkalinity in this case is the measure of the alkalinity.

Hardness: 100 cubic centimeters of the treated water is used for this test, one cubic centimeter of the soap solution corresponding to one degree of hardness. The soap solution is added a very little at a time and the whole violently shaken. Enough of the solution must be added to make a permanent lather or foam, that is, the soap bubbles must not disappear after the shaking is stopped.

Excess of lime as determined by nitrate of silver: If there is an excess of lime used in the treatment, a sample will become a dark brown by the addition of a small quantity of silver nitrate, otherwise a milky white solution will be formed.

Combined Heat and Chemical Treatment: Heat is used in many systems of feed treatment apparatus as an adjunct to the chemical process. Heat alone will remove temporary hardness by the precipitation of carbonates of lime and magnesia and, when used in connection with the chemical process, leaves only the permanent hardness or the sulphates of lime to be taken care of by chemical treatment.

TABLE 16

REAGENTS REQUIRED IN LIME AND SODA PROCESS FOR TREATING 1000 U. S. GALLONS OF WATER PER GRAIN PER GALLON OF CONTAINED IMPURITIES[16]

+-----------------------+-----------+-----------+ | | Lime[17] | Soda[18] | | | Pounds | Pounds | +-----------------------+-----------+-----------+ | Calcium Carbonate | 0.098 | ... | | Calcium Sulphate | ... | 0.124 | | Calcium Chloride | ... | 0.151 | | Calcium Nitrate | ... | 0.104 | | Magnesium Carbonate | 0.234 | ... | | Magnesium Sulphate | 0.079 | 0.141 | | Magnesium Chloride | 0.103 | 0.177 | | Magnesium Nitrate | 0.067 | 0.115 | | Ferrous Carbonate | 0.169 | ... | | Ferrous Sulphate | 0.070 | 0.110 | | Ferric Sulphate | 0.074 | 0.126 | | Aluminum Sulphate | 0.087 | 0.147 | | Free Sulphuric Acid | 0.100 | 0.171 | | Sodium Carbonate | 0.093 | ... | | Free Carbon Dioxide | 0.223 | ... | | Hydrogen Sulphite | 0.288 | ... | +-----------------------+-----------+-----------+

The chemicals used in the ordinary lime and soda process of feed water treatment are common lime and soda. The efficiency of such apparatus will depend wholly upon the amount and character of the impurities in the water to be treated. Table 16 gives the amount of lime and soda required per 1000 gallons for each grain per gallon of the various impurities found in the water. This table is based on lime containing 90 per cent calcium oxide and soda containing 58 per cent sodium oxide, which correspond to the commercial quality ordinarily purchasable. From this table and the cost of the lime and soda, the cost of treating any water per 1000 gallons may be readily computed.

Less Usual Reagents--Barium hydrate is sometimes used to reduce permanent hardness or the calcium sulphate component. Until recently, the high cost of barium hydrate has rendered its use prohibitive but at the present it is obtained as a by-product in cement manufacture and it may be purchased at a more reasonable figure than heretofore. It acts directly on the soluble sulphates to form barium sulphate which is insoluble and may be precipitated. Where this reagent is used, it is desirable that the reaction be allowed to take place outside of the boiler, though there are certain cases where its internal use is permissible.

Barium carbonate is sometimes used in removing calcium sulphate, the products of the reaction being barium sulphate and calcium carbonate, both of which are insoluble and may be precipitated. As barium carbonate in itself is insoluble, it cannot be added to water as a solution and its use should, therefore, be confined to treatment outside of the boiler.

Silicate of soda will precipitate calcium carbonate with the formation of a gelatinous silicate of lime and carbonate of soda. If calcium sulphate is also present, carbonate of soda is formed in the above reaction, which in turn will break down the sulphate.

Oxalate of soda is an expensive but efficient reagent which forms a precipitate of calcium oxalate of a particularly insoluble nature.