Page:EB1911 - Volume 11.djvu/500

 series of absorption pipettes. A convenient form of measuring vessel is that devised by W. Hempel. It consists of two vertical tubes provided with feet and connected at the bottom by flexible rubber tubing. One tube, called the “measuring tube,” is provided with a capillary stopcock at the top and graduated downwards; the other tube, called the “level tube,” is plain and open. To use the apparatus, the measuring tube is completely filled with water by pouring water into both tubes, raising the level tube until water overflows at the stopcock, which is then turned. The test gas is brought to the stopcock, by means of a fine tube which has been previously filled with water or in which the air has been displaced by running the gas through. By opening the stopcock and lowering the level tube any desired quantity of the gas can be aspirated over. In cases where a large quantity of gas, i.e. sufficient for several tests, is to be collected, the measuring tube is replaced by a large bottle. The volume of the gas in the measuring tube is determined by bringing the water in both tubes to the same level, and reading the graduation on the tube, avoiding parallax and the other errors associated with recording the coincidence of a graduation with a meniscus. The temperature and atmospheric pressure are simultaneously noted. If the tests be carried out rapidly, the temperature and pressure may be assumed to be constant, and any diminution in volume due to the absorption of a constituent may be readily expressed as a percentage. If, however, the temperature and pressure vary, the volumes are reduced to 0° and 760 mm. by means of the formula V0 = V(P − p)/(1 + .00366t)760, in which V is the observed volume, P the barometric pressure, p the vapour tension of water at the temperature t of the experiment. This reduction is facilitated by the use of tables.

Some common forms of absorption pipettes are shown in figs. 1 and 2. The simpler form consists of two bulbs connected at the bottom by a wide tube. The lower bulb is provided with a smaller bulb bearing a capillary through which the gas is led to the apparatus, the higher bulb has a wider outlet tube. The arrangement is mounted vertically on a stand. Sometimes the small bulb on the left is omitted. The form of the pipette varies with the nature of the absorbing material. For solutions which remain permanent in air the two-bulbed form suffices; in other cases a composite pipette (fig. 2) is employed, in which the absorbent is protected by a second pipette containing water. In the case of solid reagents, e.g. phosphorus, the absorbing bulb has a tubulure at the bottom. To use a pipette, the absorbing liquid is brought to the outlet of the capillary by tilting or by squeezing a rubber ball fixed to the wide end, and the liquid is maintained there by closing with a clip. The capillary is connected with the measuring tube by a fine tube previously filled with water. The clip is removed, the stopcock opened, and the level tube of the measuring apparatus raised, so that the gas passes into the first bulb. There it is allowed to remain, the pipette being shaken from time to time. It is then run back into the measuring tube by lowering the level tube, the stopcock is closed, and the volume noted. The operation is repeated until there is no further absorption.

The choice of absorbents and the order in which the gases are to be estimated is strictly limited. Confining ourselves to cases where titration methods are not employed, the general order is as follows: carbon dioxide, olefines, oxygen, carbon monoxide, hydrogen, methane and nitrogen (by difference). This scheme is particularly applicable to coal-gas. Carbon dioxide is absorbed by a potash solution containing one part of potash to between two and three of water; the stronger solution absorbs about 40 volumes of the gas. The olefines—ethylene, &c.—are generally absorbed by a very strong sulphuric acid prepared by adding sulphur trioxide to sulphuric acid to form a mixture which solidifies when slightly cooled. Bromine water is also employed. Oxygen is absorbed by stick phosphorus contained in a tubulated pipette filled with water. The temperature must be above 18°; and the absorption is prevented by ammonia, olefines, alcohol, and some other substances. An alkaline solution of pyrogallol is also used; this solution rapidly absorbs oxygen, becoming black in colour, and it is necessary to prepare the solution immediately before use. Carbon monoxide is absorbed by a solution of cuprous chloride in hydrochloric acid or, better, in ammonia. When small in amount, it is better to estimate as carbon dioxide by burning with oxygen and absorbing in potash; when large in amount, the bulk is absorbed in ammoniacal cuprous chloride and the residue burned. Hydrogen may be estimated by absorption by heated palladium contained in a capillary through which the gas is passed, or by exploding (under reduced pressure) with an excess of oxygen, and measuring the diminution in volume, two-thirds of which is the volume of hydrogen. The explosion method is unsatisfactory when the gas is contained over water, and is improved by using mercury. Methane cannot be burnt in this way even when there is much hydrogen present, and several other methods have been proposed, such as mixing with air and aspirating over copper oxide heated to redness, or mixing with oxygen and burning in a platinum tube heated to redness, the carbon dioxide formed being estimated by absorption in potash. Gases soluble in water, such as ammonia, hydrochloric acid, sulphuretted hydrogen, sulphur dioxide, &c., are estimated by passing a known volume of the gas through water and titrating the solution with a standard solution. Many types of absorption vessel are in use, and the standard solutions are generally such that 1 c.c. of the solution corresponds to 1 c.c. of the gas under normal conditions. Many forms of composite gas-apparatus are in use. One of the commonest is the Orsat shown in fig. 3. The gas is measured in the graduated cylinder on the right, which is surrounded by a water jacket and provided with a levelling bottle. At the top it is connected by a capillary tube bent at right angles to a series of absorbing vessels, the connexion being effected by stopcocks. These vessels consist of two vertical cylinders joined at the bottom by a short tube. The cylinder in direct communication with the capillary is filled with glass tubes so as to expose a larger surface of the absorbing solution to the gas. The other cylinder is open to the air and serves to hold the liquid ejected from the absorbing cylinder. Any number of bulbs can be attached to the horizontal capillary; in the form illustrated there are four, the last being a hydrogen pipette in which the palladium is heated in a horizontal tube by a spirit lamp. At the end of the horizontal tube there is a three-way cock connecting with the air or an aspirator. To use the apparatus, the measuring tube is completely filled with water by raising the levelling bottle. The absorbing vessels are then about half filled with the absorbents, and, by opening the cocks and aspirating, the liquid is brought so as