Chapter IV: Part 4

The chemical compound known as H_{2}O exists in three states or conditions--ice, water and steam; the only difference between these states or conditions is in the presence or absence of a quantity of energy exhibited partly in the form of heat and partly in molecular activity, which, for want of a better name, we are accustomed to call "latent heat"; and to transform it from one state to another we have only to supply or extract heat. For instance, if we take a quantity of ice, say one pound, at absolute zero[11] and supply heat, the first effect is to raise its temperature until it arrives at a point 492 Fahrenheit degrees above the starting point. Here it stops growing warmer, though we keep on adding heat. It, however, changes from ice to water, and when we have added sufficient heat to have made it, had it remained ice, 283 degrees hotter or a temperature of 315 degrees Fahrenheit's thermometer, it has all become water, at the same temperature at which it commenced to change, namely, 492 degrees above absolute zero, or 32 degrees by Fahrenheit's scale. Let us still continue to add heat, and it will now grow warmer again, though at a slower rate--that is, it now takes about double the quantity of heat to raise the pound one degree that it did before--until it reaches a temperature of 212 degrees Fahrenheit, or 672 degrees absolute (assuming that we are at the level of the sea). Here we find another critical point. However much more heat we may apply, the water, as water, at that pressure, cannot be heated any hotter, but changes on the addition of heat to steam; and it is not until we have added heat enough to have raised the temperature of the water 966 degrees, or to 1,178 degrees by Fahrenheit's thermometer (presuming for the moment that its specific heat has not changed since it became water), that it has all become steam, which steam, nevertheless, is at the temperature of 212 degrees, at which the water began to change. Thus over four-fifths of the heat which has been added to the water has disappeared, or become insensible in the steam to any of our instruments.

It follows that if we could reduce steam at atmospheric pressure to water, without loss of heat, the heat stored within it would cause the water to be red hot; and if we could further change it to a solid, like ice, without loss of heat, the solid would be white hot, or hotter than melted steel--it being assumed, of course, that the specific heat of the water and ice remain normal, or the same as they respectively are at the freezing point.

After steam has been formed, a further addition of heat increases the temperature again at a much faster ratio to the quantity of heat added, which ratio also varies according as we maintain a constant pressure or a constant volume; and I am not aware that any other critical point exists where this will cease to be the fact until we arrive at that very high temperature, known as the point of dissociation, at which it becomes resolved into its original gases.

The heat which has been absorbed by one pound of water to convert it into a pound of steam at atmospheric pressure is sufficient to have melted 3 pounds of steel or 13 pounds of gold. This has been transformed into something besides heat; stored up to reappear as heat when the process is reversed. That condition is what we are pleased to call latent heat, and in it resides mainly the ability of the steam to do work.

[Graph: Temperature in Fahrenheit Degrees (from Absolute Zero) against Quantity of Heat in British Thermal Units]

The diagram shows graphically the relation of heat to temperature, the horizontal scale being quantity of heat in British thermal units, and the vertical temperature in Fahrenheit degrees, both reckoned from absolute zero and by the usual scale. The dotted lines for ice and water show the temperature which would have been obtained if the conditions had not changed. The lines marked "gold" and "steel" show the relation to heat and temperature and the melting points of these metals. All the inclined lines would be slightly curved if attention had been paid to the changing specific heat, but the curvature would be small. It is worth noting that, with one or two exceptions, the curves of all substances lie between the vertical and that for water. That is to say, that water has a greater capacity for heat than all other substances except two, hydrogen and bromine.

In order to generate steam, then, only two steps are required: 1st, procure the heat, and 2nd, transfer it to the water. Now, you have it laid down as an axiom that when a body has been transferred or transformed from one place or state into another, the same work has been done and the same energy expended, whatever may have been the intermediate steps or conditions, or whatever the apparatus. Therefore, when a given quantity of water at a given temperature has been made into steam at a given temperature, a certain definite work has been done, and a certain amount of energy expended, from whatever the heat may have been obtained, or whatever boiler may have been employed for the purpose.

A pound of coal or any other fuel has a definite heat producing capacity, and is capable of evaporating a definite quantity of water under given conditions. That is the limit beyond which even perfection cannot go, and yet I have known, and doubtless you have heard of, cases where inventors have claimed, and so-called engineers have certified to, much higher results.

The first step in generating steam is in burning the fuel to the best advantage. A pound of carbon will generate 14,500 British thermal units, during combustion into carbonic dioxide, and this will be the same, whatever the temperature or the rapidity at which the combustion may take place. If possible, we might oxidize it at as slow a rate as that with which iron rusts or wood rots in the open air, or we might burn it with the rapidity of gunpowder, a ton in a second, yet the total heat generated would be precisely the same. Again, we may keep the temperature down to the lowest point at which combustion can take place, by bringing large bodies of air in contact with it, or otherwise, or we may supply it with just the right quantity of pure oxygen, and burn it at a temperature approaching that of dissociation, and still the heat units given off will be neither more nor less. It follows, therefore, that great latitude in the manner or rapidity of combustion may be taken without affecting the quantity of heat generated.

But in practice it is found that other considerations limit this latitude, and that there are certain conditions necessary in order to get the most available heat from a pound of coal. There are three ways, and only three, in which the heat developed by the combustion of coal in a steam boiler furnace may be expended.

1st, and principally. It should be conveyed to the water in the boiler, and be utilized in the production of steam. To be perfect, a boiler should so utilize all the heat of combustion, but there are no perfect boilers.

2nd. A portion of the heat of combustion is conveyed up the chimney in the waste gases. This is in proportion to the weight of the gases, and the difference between their temperature and that of the air and coal before they entered the fire.

3rd. Another portion is dissipated by radiation from the sides of the furnace. In a stove the heat is all used in these latter two ways, either it goes off through the chimney or is radiated into the surrounding space. It is one of the principal problems of boiler engineering to render the amount of heat thus lost as small as possible.

The loss from radiation is in proportion to the amount of surface, its nature, its temperature, and the time it is exposed. This loss can be almost entirely eliminated by thick walls and a smooth white or polished surface, but its amount is ordinarily so small that these extraordinary precautions do not pay in practice.

It is evident that the temperature of the escaping gases cannot be brought below that of the absorbing surfaces, while it may be much greater even to that of the fire. This is supposing that all of the escaping gases have passed through the fire. In case air is allowed to leak into the flues, and mingle with the gases after they have left the heating surfaces, the temperature may be brought down to almost any point above that of the atmosphere, but without any reduction in the amount of heat wasted. It is in this way that those low chimney temperatures are sometimes attained which pass for proof of economy with the unobserving. All surplus air admitted to the fire, or to the gases before they leave the heating surfaces, increases the losses.

We are now prepared to see why and how the temperature and the rapidity of combustion in the boiler furnace affect the economy, and that though the amount of heat developed may be the same, the heat available for the generation of steam may be much less with one rate or temperature of combustion than another.

Assuming that there is no air passing up the chimney other than that which has passed through the fire, the higher the temperature of the fire and the lower that of the escaping gases the better the economy, for the losses by the chimney gases will bear the same proportion to the heat generated by the combustion as the temperature of those gases bears to the temperature of the fire. That is to say, if the temperature of the fire is 2500 degrees and that of the chimney gases 500 degrees above that of the atmosphere, the loss by the chimney will be 500/2500 = 20 per cent. Therefore, as the escaping gases cannot be brought below the temperature of the absorbing surface, which is practically a fixed quantity, the temperature of the fire must be high in order to secure good economy.

The losses by radiation being practically proportioned to the time occupied, the more coal burned in a given furnace in a given time, the less will be the proportionate loss from that cause.

It therefore follows that we should burn our coal rapidly and at a high temperature to secure the best available economy.

PROPERTIES OF WATER

Pure water is a chemical compound of one volume of oxygen and two volumes of hydrogen, its chemical symbol being H_{2}O.

The weight of water depends upon its temperature. Its weight at four temperatures, much used in physical calculations, is given in Table 10.

TABLE 10

WEIGHT OF WATER AT TEMPERATURES
USED IN PHYSICAL CALCULATIONS

+---------------------------+----------+----------+ | Temperature Degrees |Weight per|Weight per| | Fahrenheit |Cubic Foot|Cubic Inch| | | Pounds | Pounds | +---------------------------+----------+----------+ |At 32 degrees or freezing | | | | point at sea level | 62.418 | 0.03612 | |At 39.2 degrees or point of| | | | maximum density | 62.427 | 0.03613 | |At 62 degrees or standard | | | | temperature | 62.355 | 0.03608 | |At 212 degrees or boiling | | | | point at sea level | 59.846 | 0.03469 | +---------------------------+----------+----------+

While authorities differ as to the weight of water, the range of values given for 62 degrees Fahrenheit (the standard temperature ordinarily taken) being from 62.291 pounds to 62.360 pounds per cubic foot, the value 62.355 is generally accepted as the most accurate.

A United States standard gallon holds 231 cubic inches and weighs, at 62 degrees Fahrenheit, approximately 8-1/3 pounds.

A British Imperial gallon holds 277.42 cubic inches and weighs, at 62 degrees Fahrenheit, 10 pounds.

The above are the true weights corrected for the effect of the buoyancy of the air, or the weight in vacuo. If water is weighed in air in the ordinary way, there is a correction of about one-eighth of one per cent which is usually negligible.

TABLE 11

VOLUME AND WEIGHT OF DISTILLED WATER AT
VARIOUS TEMPERATURES[12]

+-----------+---------------+----------+ |Temperature|Relative Volume|Weight per| | Degrees | Water at 39.2 |Cubic Foot| | Fahrenheit| Degrees = 1 | Pounds | +-----------+---------------+----------+ | 32 | 1.000176 | 62.42 | | 39.2 | 1.000000 | 62.43 | | 40 | 1.000004 | 62.43 | | 50 | 1.00027 | 62.42 | | 60 | 1.00096 | 62.37 | | 70 | 1.00201 | 62.30 | | 80 | 1.00338 | 62.22 | | 90 | 1.00504 | 62.11 | | 100 | 1.00698 | 62.00 | | 110 | 1.00915 | 61.86 | | 120 | 1.01157 | 61.71 | | 130 | 1.01420 | 61.55 | | 140 | 1.01705 | 61.38 | | 150 | 1.02011 | 61.20 | | 160 | 1.02337 | 61.00 | | 170 | 1.02682 | 60.80 | | 180 | 1.03047 | 60.58 | | 190 | 1.03431 | 60.36 | | 200 | 1.03835 | 60.12 | | 210 | 1.04256 | 59.88 | | 212 | 1.04343 | 59.83 | | 220 | 1.0469 | 59.63 | | 230 | 1.0515 | 59.37 | | 240 | 1.0562 | 59.11 | | 250 | 1.0611 | 58.83 | | 260 | 1.0662 | 58.55 | | 270 | 1.0715 | 58.26 | | 280 | 1.0771 | 57.96 | | 290 | 1.0830 | 57.65 | | 300 | 1.0890 | 57.33 | | 310 | 1.0953 | 57.00 | | 320 | 1.1019 | 56.66 | | 330 | 1.1088 | 56.30 | | 340 | 1.1160 | 55.94 | | 350 | 1.1235 | 55.57 | | 360 | 1.1313 | 55.18 | | 370 | 1.1396 | 54.78 | | 380 | 1.1483 | 54.36 | | 390 | 1.1573 | 53.94 | | 400 | 1.167 | 53.5 | | 410 | 1.177 | 53.0 | | 420 | 1.187 | 52.6 | | 430 | 1.197 | 52.2 | | 440 | 1.208 | 51.7 | | 450 | 1.220 | 51.2 | | 460 | 1.232 | 50.7 | | 470 | 1.244 | 50.2 | | 480 | 1.256 | 49.7 | | 490 | 1.269 | 49.2 | | 500 | 1.283 | 48.7 | | 510 | 1.297 | 48.1 | | 520 | 1.312 | 47.6 | | 530 | 1.329 | 47.0 | | 540 | 1.35 | 46.3 | | 550 | 1.37 | 45.6 | | 560 | 1.39 | 44.9 | +-----------+---------------+----------+

Water is but slightly compressible and for all practical purposes may be considered non-compressible. The coefficient of compressibility ranges from 0.000040 to 0.000051 per atmosphere at ordinary temperatures, this coefficient decreasing as the temperature increases.

Table 11 gives the weight in vacuo and the relative volume of a cubic foot of distilled water at various temperatures.

The weight of water at the standard temperature being taken as 62.355 pounds per cubic foot, the pressure exerted by the column of water of any stated height, and conversely the height of any column required to produce a stated pressure, may be computed as follows:

The pressure in pounds per square foot = 62.355 × height of column in feet.

The pressure in pounds per square inch = 0.433 × height of column in feet.

Height of column in feet = pressure in pounds per square foot ÷ 62.355.

Height of column in feet = pressure in pounds per square inch ÷ 0.433.

Height of column in inches = pressure in pounds per square inch × 27.71.

Height of column in inches = pressure in ounces per square inch × 1.73.

By a change in the weights given above, the pressure exerted and height of column may be computed for temperatures other than 62 degrees.

A pressure of one pound per square inch is exerted by a column of water 2.3093 feet or 27.71 inches high at 62 degrees Fahrenheit.

Water in its natural state is never found absolutely pure. In solvent power water has a greater range than any other liquid. For common salt, this is approximately a constant at all temperatures, while with such impurities as magnesium and sodium sulphates, this solvent power increases with an increase in temperature.

TABLE 12

BOILING POINT OF WATER AT VARIOUS ALTITUDES

+--------------+----------------+-------------+---------------+ |Boiling Point | Altitude Above | Atmospheric | Barometer | | Degrees | Sea Level | Pressure | Reduced | | Fahrenheit | Feet | Pounds per | to 32 Degrees | | | | Square Inch | Inches | +--------------+----------------+-------------+---------------+ | 184 | 15221 | 8.20 | 16.70 | | 185 | 14649 | 8.38 | 17.06 | | 186 | 14075 | 8.57 | 17.45 | | 187 | 13498 | 8.76 | 17.83 | | 188 | 12934 | 8.95 | 18.22 | | 189 | 12367 | 9.14 | 18.61 | | 190 | 11799 | 9.34 | 19.02 | | 191 | 11243 | 9.54 | 19.43 | | 192 | 10685 | 9.74 | 19.85 | | 193 | 10127 | 9.95 | 20.27 | | 194 | 9579 | 10.17 | 20.71 | | 195 | 9031 | 10.39 | 21.15 | | 196 | 8481 | 10.61 | 21.60 | | 197 | 7932 | 10.83 | 22.05 | | 198 | 7381 | 11.06 | 22.52 | | 199 | 6843 | 11.29 | 22.99 | | 200 | 6304 | 11.52 | 23.47 | | 201 | 5764 | 11.76 | 23.95 | | 202 | 5225 | 12.01 | 24.45 | | 203 | 4697 | 12.26 | 24.96 | | 204 | 4169 | 12.51 | 25.48 | | 205 | 3642 | 12.77 | 26.00 | | 206 | 3115 | 13.03 | 26.53 | | 207 | 2589 | 13.30 | 27.08 | | 208 | 2063 | 13.57 | 27.63 | | 209 | 1539 | 13.85 | 28.19 | | 210 | 1025 | 14.13 | 28.76 | | 211 | 512 | 14.41 | 29.33 | | 212 | Sea Level | 14.70 | 29.92 | +--------------+----------------+-------------+---------------+

Sea water contains on an average approximately 3.125 per cent of its weight of solid matter or a thirty-second part of the weight of the water and salt held in solution. The approximate composition of this solid matter will be: sodium chloride 76 per cent, magnesium chloride 10 per cent, magnesium sulphate 6 per cent, calcium sulphate 5 per cent, calcium carbonate 0.5 per cent, other substances 2.5 per cent.

The boiling point of water decreases as the altitude above sea level increases. Table 12 gives the variation in the boiling point with the altitude.

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

+-----------------------+--------------+-----------------------------+ | Difficulty Resulting | Nature of | Ordinary Method of | | from Presence of | Difficulty | Overcoming or Relieving | +-----------------------+--------------+-----------------------------+ | Sediment, Mud, etc. | Incrustation | Settling tanks, filtration, | | | | blowing down. | | | | | | Readily Soluble Salts | Incrustation | Blowing down. | | | | | | Bicarbonates of Lime, | Incrustation | Heating feed. Treatment by | | Magnesia, etc. | | addition of lime or of lime | | | | and soda. Barium carbonate. | | | | | | Sulphate of Lime | Incrustation | Treatment by addition of | | | | soda. Barium carbonate. | | | | | | Chloride and Sulphate | Corrosion | Treatment by addition of | | of Magnesium | | carbonate of soda. | | | | | | Acid | Corrosion | Alkali. | | | | | | Dissolved Carbonic | Corrosion | Heating feed. Keeping air | | Acid and Oxygen | | from feed. Addition of | | | | caustic soda or slacked | | | | lime. | | | | | | Grease | Corrosion | Filter. Iron alum as | | | | coagulent. Neutralization | | | | by carbonate of soda. Use | | | | of best hydrocarbon oils. | | | | | | Organic Matter | Corrosion | Filter. Use of coagulent. | | | | | | Organic Matter | Priming | Settling tanks. Filter in | | (Sewage) | | connection with coagulent. | | | | | | Carbonate of Soda in | Priming | Barium carbonate. New feed | | large quantities | | supply. If from treatment, | | | | change. | +-----------------------+--------------+-----------------------------+

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

+------------------------------+------------+-------------+ |Temperature Degrees Fahrenheit| 60 Degrees | 212 Degrees | +------------------------------+------------+-------------+ |Calcium Carbonate | 2.5 | 1.5 | |Calcium Sulphate | 140.0 | 125.0 | |Magnesium Carbonate | 1.0 | 1.8 | |Magnesium Sulphate | 3.0 pounds | 12.0 pounds | |Sodium Chloride | 3.5 pounds | 4.0 pounds | |Sodium Sulphate | 1.1 pounds | 5.0 pounds | +------------------------------+------------+-------------+

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.

Alum and iron alum will act as efficient coagulents where organic matter is present in the water. Iron alum has not only this property but also that of reducing oil discharged from surface condensers to a condition in which it may be readily removed by filtration.

Corrosion--Where there is a corrosive action because of the presence of acid in the water or of oil containing fatty acids which will decompose and cause pitting wherever the sludge can find a resting place, it may be overcome by the neutralization of the water by carbonate of soda. Such neutralization should be carried to the point where the water will just turn red litmus paper blue. As a preventative of such action arising from the presence of the oil, only the highest grades of hydrocarbon oils should be used.

Acidity will occur where sea water is present in a boiler. There is the possibility of such an occurrence in marine practice and in stationary plants using sea water for condensing, due to leaky condenser tubes, priming in the evaporators, etc. Such acidity is caused through the dissociation of magnesium chloride into hydrochloride acid and magnesia under high temperatures. The acid in contact with the metal forms an iron salt which immediately upon its formation is neutralized by the free magnesia in the water, thereby precipitating iron oxide and reforming magnesium chloride. The preventive for corrosion arising from such acidity is the keeping tight of the condenser. Where it is unavoidable that some sea water should find its way into a boiler, the acidity resulting should be neutralized by soda ash. This will convert the magnesium chloride into magnesium carbonate and sodium chloride, neither of which is corrosive but both of which are scale-forming.

The presence of air in the feed water which is sucked in by the feed pump is a well recognized cause of corrosion. Air bubbles form below the water line and attack the metal of the boiler, the oxygen of the air causing oxidization of the boiler metal and the formation of rust. The particle of rust thus formed is swept away by the circulation or is dislodged by expansion and the minute pit thus left forms an ideal resting place for other air bubbles and the continuation of the oxidization process. The prevention is, of course, the removing of the air from the feed water. In marine practice, where there has been experienced the most difficulty from this source, it has been found to be advantageous to pump the water from the hot well to a filter tank placed above the feed pump suction valves. In this way the air is liberated from the surface of the tank and a head is assured for the suction end of the pump. In this same class of work, the corrosive action of air is reduced by introducing the feed through a spray nozzle into the steam space above the water line.

Galvanic action, resulting in the eating away of the boiler metal through electrolysis was formerly considered practically the sole cause of corrosion. But little is known of such action aside from the fact that it does take place in certain instances. The means adopted as a remedy is usually the installation of zinc plates within the boiler, which must have positive metallic contact with the boiler metal. In this way, local electrolytic effects are overcome by a still greater electrolytic action at the expense of the more positive zinc. The positive contact necessary is difficult to maintain and it is questionable just what efficacy such plates have except for a short period after their installation when the contact is known to be positive. Aside from protection from such electrolytic action, however, the zinc plates have a distinct use where there is the liability of air in the feed, as they offer a substance much more readily oxidized by such air than the metal of the boiler.

Foaming--Where foaming is caused by organic matter in suspension, it may be largely overcome by filtration or by the use of a coagulent in connection with filtration, the latter combination having come recently into considerable favor. Alum, or potash alum, and iron alum, which in reality contains no alumina and should rather be called potassia-ferric, are the coagulents generally used in connection with filtration. Such matter as is not removed by filtration may, under certain conditions, be handled by surface blowing. In some instances, settling tanks are used for the removal of matter in suspension, but where large quantities of water are required, filtration is ordinarily substituted on account of the time element and the large area necessary in settling tanks.

Where foaming occurs as the result of overtreatment of the feed water, the obvious remedy is a change in such treatment.

Priming--Where priming is caused by excessive concentration of salts within a boiler, it may be overcome largely by frequent blowing down. The degree of concentration allowable before priming will take place varies widely with conditions of operation and may be definitely determined only by experience with each individual set of conditions. It is the presence of the salts that cause priming that may result in the absolute unfitness of water for boiler feed purposes. Where these salts exist in such quantities that the amount of blowing down necessary to keep the degree of concentration below the priming point results in excessive losses, the only remedy is the securing of another supply of feed, and the results will warrant the change almost regardless of the expense. In some few instances, the impurities may be taken care of by some method of water treatment but such water should be submitted to an authority on the subject before any treatment apparatus is installed.

Boiler Compounds--The method of treatment of feed water by far the most generally used is by the use of some of the so-called boiler compounds. There are many reliable concerns handling such compounds who unquestionably secure the promised results, but there is a great tendency toward looking on the compound as a "cure all" for any water difficulties and care should be taken to deal only with reputable concerns.

The composition of these compounds is almost invariably based on soda with certain tannic substances and in some instances a gelatinous substance which is presumed to encircle scale particles and prevent their adhering to the boiler surfaces. The action of these compounds is ordinarily to reduce the calcium sulphate in the water by means of carbonate of soda and to precipitate it as a muddy form of calcium carbonate which may be blown off. The tannic compounds are used in connection with the soda with the idea of introducing organic matter into any scale already formed. When it has penetrated to the boiler metal, decomposition of the scale sets in, causing a disruptive effect which breaks the scale from the metal sometimes in large slabs. It is this effect of boiler compounds that is to be most carefully guarded against or inevitable trouble will result from the presence of loose scale with the consequent danger of tube losses through burning.

When proper care is taken to suit the compound to the water in use, the results secured are fairly effective. In general, however, the use of compounds may only be recommended for the prevention of scale rather than with the view to removing scale which has already formed, that is, the compounds should be introduced with the feed water only when the boiler has been thoroughly cleaned.

FEED WATER HEATING AND METHODS OF FEEDING

Before water fed into a boiler can be converted into steam, it must be first heated to a temperature corresponding to the pressure within the boiler. Steam at 160 pounds gauge pressure has a temperature of approximately 371 degrees Fahrenheit. If water is fed to the boiler at 60 degrees Fahrenheit, each pound must have 311 B. t. u. added to it to increase its temperature 371 degrees, which increase must take place before the water can be converted into steam. As it requires 1167.8 B. t. u. to raise one pound of water from 60 to 371 degrees and to convert it into steam at 160 pounds gauge pressure, the 311 degrees required simply to raise the temperature of the water from 60 to 371 degrees will be approximately 27 per cent of the total. If, therefore, the temperature of the water can be increased from 60 to 371 degrees before it is introduced into a boiler by the utilization of heat from some source that would otherwise be wasted, there will be a saving in the fuel required of 311 ÷ 1167.8 = 27 per cent, and there will be a net saving, provided the cost of maintaining and operating the apparatus for securing this saving is less than the value of the heat thus saved.

The saving in the fuel due to the heating of feed water by means of heat that would otherwise be wasted may be computed from the formula:

100 (t - t_{i})
Fuel saving per cent = --------------- (1)
H + 32 - t_{i}

where, t = temperature of feed water after heating, t_{i} = temperature of feed water before heating, and H = total heat above 32 degrees per pound of steam at the boiler pressure. Values of H may be found in Table 23. Table 17 has been computed from this formula to show the fuel saving under the conditions assumed with the boiler operating at 180 pounds gauge pressure.

TABLE 17

SAVING IN FUEL, IN PER CENT, BY HEATING FEED WATER
GAUGE PRESSURE 180 POUNDS

+-----------+-----------------------------------------+ | Initial | Final Temperature--Degrees Fahrenheit | |Temperature|-----+-----+-----+-----+-----+-----+-----| | Fahrenheit| 120 | 140 | 160 | 180 | 200 | 250 | 300 | +-----------+-----+-----+-----+-----+-----+-----+-----+ | 32 | 7.35| 9.02|10.69|12.36|14.04|18.20|22.38| | 35 | 7.12| 8.79|10.46|12.14|13.82|18.00|22.18| | 40 | 6.72| 8.41|10.09|11.77|13.45|17.65|21.86| | 45 | 6.33| 8.02| 9.71|11.40|13.08|17.30|21.52| | 50 | 5.93| 7.63| 9.32|11.02|12.72|16.95|21.19| | 55 | 5.53| 7.24| 8.94|10.64|12.34|16.60|20.86| | 60 | 5.13| 6.84| 8.55|10.27|11.97|16.24|20.52| | 65 | 4.72| 6.44| 8.16| 9.87|11.59|15.88|20.18| | 70 | 4.31| 6.04| 7.77| 9.48|11.21|15.52|19.83| | 75 | 3.90| 5.64| 7.36| 9.09|10.82|15.16|19.48| | 80 | 3.48| 5.22| 6.96| 8.70|10.44|14.79|19.13| | 85 | 3.06| 4.80| 6.55| 8.30|10.05|14.41|18.78| | 90 | 2.63| 4.39| 6.14| 7.89| 9.65|14.04|18.43| | 95 | 2.20| 3.97| 5.73| 7.49| 9.25|13.66|18.07| | 100 | 1.77| 3.54| 5.31| 7.08| 8.85|13.28|17.70| | 110 | .89| 2.68| 4.47| 6.25| 8.04|12.50|16.97| | 120 | .00| 1.80| 3.61| 5.41| 7.21|11.71|16.22| | 130 | | .91| 2.73| 4.55| 6.37|10.91|15.46| | 140 | | .00| 1.84| 3.67| 5.51|10.09|14.68| | 150 | | | .93| 2.78| 4.63| 9.26|13.89| | 160 | | | .00| 1.87| 3.74| 8.41|13.09| | 170 | | | | .94| 2.83| 7.55|12.27| | 180 | | | | .00| 1.91| 6.67|11.43| | 190 | | | | | .96| 5.77|10.58| | 200 | | | | | .00| 4.86| 9.71| | 210 | | | | | | 3.92| 8.82| +-----------+-----+-----+-----+-----+-----+-----+-----+

Besides the saving in fuel effected by the use of feed water heaters, other advantages are secured. The time required for the conversion of water into steam is diminished and the steam capacity of the boiler thereby increased. Further, the feeding of cold water into a boiler has a tendency toward the setting up of temperature strains, which are diminished in proportion as the temperature of the feed approaches that of the steam. An important additional advantage of heating feed water is that in certain types of heaters a large portion of the scale forming ingredients are precipitated before entering the boiler, with a consequent saving in cleaning and losses through decreased efficiency and capacity.

In general, feed water heaters may be divided into closed heaters, open heaters and economizers; the first two depend for their heat upon exhaust, or in some cases live steam, while the last class utilizes the heat of the waste flue gases to secure the same result. The question of the type of apparatus to be installed is dependent upon the conditions attached to each individual case.