B.

Dissolved
In this section, methods are given for determining three gases commonly associated with industrial water and treating plants.

1. Determination of Ammonia in Condensates

The corrosive effect of oxygen on copper is greatly enhanced in the presence of ammonia because of the stability of the cupric ammonia complex ion C U ( N H ~ ) ~ + + :
CU t 4 N H 3 tJi0, t H ,O=Cu(NH,),(OH)

This reaction can cause severe corrosion in cooling systems with heat exchangers constructed of admiralty, aluminum bronze, or other alloys containing copper. Treatment with chromate or chromate-polyphosphate gives good protection, however, and even water containing 100 ppm NH, from a cooling system in an ammonia manufacturing plant was found to contain less than 0.2 ppm copper. Hydrazine is used as an oxygen scavenger, usually in boilers operated at very high pressures, and ammonia and nitrogen are produced in a dismutation reaction :
3N2H4=4NH3+N2

In general, hydrazine is not easily reduced to ammonia, but the following reaction may be of significance in an acidic environment.
N, H 3+tFei~3=Fetf+~N t N H 4 +t H t

In the following section, a procedure is given for estimating ammonia in condensate. Accurate determinations of ammonia require elaborate procedures (34) that are seldom applied for routine control. For most purposes, it is only necessary to ascertain that a condensate has enough ammonia (or amine) to protect the system against corrosion by carbonic acid. To determine the concentration of ammonia in process waters, it is usually sufficient to make the sample alkaline and steam-distil
98

6. DISSOLVED GASES

99

the ammonia into a dilute solution of neutralized boric acid (58). If hydrogen sulfide is present, as is often the case, bromocresol green is recommended as the indicator in the final acidimetric titration. A very convenient steam generator and collection system is manufactured by the Rinco instrument Company, Inc." See Part IV, Section E, p. 280, for an example of the use of determinations of ammonia in interpreting the analyses of certain corrosion deposits. Nessler's reagent, an alkaline solution of potassium tetraiodomercurate, has been much criticized for its shortcomings as a colorimetric reagent for ammonia. Vanselow (59), however, has presented a study of the factors involved in preparing a reagent producing a consistent stable color with ammonia without forming objectionable precipitates. Consideration of the equation
NH 3+2Hg14'+30H-=71-+HgOH *NH*HgI+2H , O

indicates that increasing the concentration of hydroxide would increase the color, while increasing the iodide concentration would decrease the color. The rates of formation of the color are similarly affected. For the preparation of the reagent, Vanselow recommends ten moles of hydroxide per equivalent of mercuric ion with a 5% excess of iodide over that required by the formula K,Hg14. The preparation of Nessler's reagent according to these recommendations produces an exceptionally stable reagent. There is some difference of opinion as to the formula of the colloidal orange-red compound produced with ammonia. Vanselow (59) gives the formula used in the equation above, while Nichols and Willets (60) formulate the reaction in two steps as follows:
2K ,Hg I

+ 2N H , = 2 ( N H ,Hg I ) , +4 KI ) = N H ,Hg nl , + N H dl 2( NH ,Hgl ,

+2NH = NH 2Hg , I 3+4KI

The net reaction is:

2K ,Hgl

+ NH dl

Latimer and Hildebrand (61) consider the product to be the iodide of Millon's base (Hg,NOH*H,O) and formulate it as Hg,NI*H,O. Liebhafsky and Bronk (6) have noted that various aliphatic and
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PART II

THE ANALYSIS OF INDUSTRIAL WATERS

aromatic amines including phenyl-a-naphthylamine, aniline, diamylamine, propylenediamine, triethylamine, and diphenylamine give colors with Nessler's reagent that develop more slowly, but eventually become more intense than an equivalent amount of ammonia. In some instances this fact may have t o be taken into account in interpreting results by the procedure given here. PR E PA RAT10 N (1) Reagent: Nessler's Reagent. Dissolve 34.9 g of KI in 100 ml of water and gradually add 45.5 g of Hgl,, stirring until solution is complete. Dissolve 112 g of KOH in 200 ml of water and cool to room temperature. Pour the t w o solutions together and dilute t o 1000 ml with water. Allow the solution t o stand 2-3 days before using to allow the small amount of precipitate to settle. Standard Ammonia Solution. Dissolve 0.31 4 g of NH,CI in 1000 ml of water. (1 ml=0.10 mg NH3.) (2) Standardization: 1. Dilute the standard ammonia solution tenfold to produce a solution containing .01 mg NH3/ml. Transfer 2.0, 4.0, 6.0, 8.0, and 10.0 ml of this solution to a series of 100-ml volumetric flasks and include a blank. 2. Dilute the solution in each flask t o about 75 ml, then add 5.0 rnl of Nessler's reagent t o each flask while swirling. Dilute t o volume and mix well. 3. Let the solutions stand 30 minutes and then determine the transmittances of each solution at 420 m p against the blank solution using 50-mm cuvettes. 4. Plot the milligrams of N H 3 against the corresponding transmittances on semilogarithmic graph paper." PROCEDUR Et 1. Transfer a measured sample1 of condensate to a 100-ml volumetric flask and also prepare a blank with distilled water. 2. Add 5.0 ml of Nessler's reagent to sample and blank and mix well. 3. Allow the solutions to stand 30 minutes, then determine the
If desired, prepare a calibration curve using 10-mm cuvettes covering the range 0.1 -0.5 mg of ammonia.

Samples producing precipitates must be distilled and titrated acidimetrically, as mentioned in the discussion. 1 A 95-ml sample covers the range 0.2-5 ppm NH 3, the usual range for condensate.

B. DISSOLVED GASES

101

transmittance of the sample against the blank at 420 mp, using whichever cuvette is appropriate for the intensity of color obtained. 4. From the appropriate calibration curve read the corresponding milligrams of ammonia :
ppm N H , = mg N H , X ~ O ~ ml sample x 103

2.

Determination of Carbon Dioxide

Carbon dioxide is objectionable because of its corrosive effect in pipelines used for returning condensate. Corrosion by carbon dioxide is evidenced by typi'cal grooving in the surface of the metal and is particularly severe at bends and threads where the metal is stressed. The use of ammonia or amines to prevent corrosion by carbon dioxide is discussed in Part I, p. 31. These compounds raise the pH of the condensate eliminating the oxidizing effect of hydrogen ion. Most analytical methods are concerned with determining total carbon dioxide. McKinney and Amorosi (63) have described a volumetric procedure that is useful if ferrous ion, ammonia, hydrogen sulfide, and colored material are absent. Clarke (64) has developed an evolution method that was later improved by Smith et al. (65) t o permit determinations of carbon dioxide at less than 1.5 ppm concentration. The latter procedure was devised for checking the efficiency of deaerating heaters and demineralizers used for producing carbon dioxide-free feed water for boilers. The hydrolysis of bicarbonate in a boiler produces carbon dioxide which escapes with the steam :
HC0,-+H,O=H,CO,+OH-

The gas eventually dissolves in the condensate, which is customarily deaerated before being reused for feed water. As carbon dioxide is removed in the deaerator, the pH of the water rises. If it is necessary to determine the actual concentration of carbon dioxide present in a water sample, the most convenient way is by use of a nomograph relating temperature, total solids, pH, and alkalinity to the equilibrium concentration of carbon dioxide. A set of such nomographs is available from the American Water Works Association.*
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102

PART I1

THE ANALYSIS OF INDUSTRIAL WATERS

For the routine control of water-treating systems the determination of carbon dioxide is seldom required. A simple procedure is included here, however, which is applicable to some water supplies, particularly well waters, that contain dissolved carbon dioxide. The method consists of titrating a freshly-drawn sample to phenolphthalein with standard alkali. As the reaction between CO, and O H - is slow (66),the former is always partially lost during the titration. It is, therefore, necessary to repeat the titration adding all at once the amount of alkali added in the first titration.
COz+OH-=HCO,(slow)

H ,CO,+OH-==HCO,-+H

,O

(rapid)

PROCEDURE 1. Connect a length of tubing to the sampling valve, place the other end of the tube in the bottom of a 100-mi graduated cylinder, and allow the water to flow for a few minutes. 2. Withdraw the tube with the water flowing and adjust the volume to the 100-ml mark. 3. Add a few drops of phenolphthalein indicator solution and titrate with a standard solution of sodium hydroxide* while stirring with a long glass rod until the color persists for five minutes. 4. Draw a second sample using the same procedure, then add rapidly the volume of standard sodium hydroxide used in the first titration and complete the titration to phenolphthalein. Use the total volume of the second titretion to calculate the content of carbon di0xide.t
p p m CO,=-titr x N x 4 4 x l o a ____ m l sample x 103

3.

Determination of Oxygen

Dissolved oxygen is normally determined in boiler feed water, and as sodium sulfite is so widely used as a scavenger, the following procedure is so arranged that either oxygen or sodium sulfite
____-~ If p p m C o t is desired it is convenient t o use N / 4 4 NaOH; for ppm CaCOs use N / 5 0 NaOH. Should free mineral acidity be present, titrate first t o methyl orange then t o phenolphthalein. Repeat, and use the difference between the t w o end points t o calculate free carbon dioxide.

B. DISSOLVED GASES

103

can be determined in one sampling. They do not, of course, occur simultaneously in a water sample. The procedure given here is one of many modifications of the Winkler method (67). Manganous sulfate, alkaline potassium iodide, and sulfuric acid are added, in the order named, to measured volumes of the sample protected from exposure to air. If necessary, potassium bi-iodate is added, and the liberated iodine is titrated with standard sodium thiosulfate. The reactions involved in the t w o cases that can occur are as follows: (a) Oxygen
2H20+4Mn(OH) ,+O2=4Mn(OH) 2Mn++++31-=I 3-+2Mn'f 6H++1O3-+81-=3I3-+3H20

(11
(2) (3)

(b)

Sulfite
No reaction
No reaction

(1)
(2) (3)

2Hf+310 3-+121-+4H

,SO S=513-+4SO,=+5HzO

These reactions show that 4 moles S 2 0 3 = = l mole 02, and 2 moles S z 0 3 ' = l mole Na,S03. The equivalent weight of oxygen is therefore 8 and that of sodium sulfite 63. PREPARATION

(1 ) Reagents : Manganous Sulfate Solution. g of MnSO,*H,O in 1000-ml of water.

Dissolve 364

Alkaline Potassium Iodide Solution. (1) Dissolve 700 g of KOH in 450 ml of water and cool. (2) Dissolve 150 g of KI in 150 ml of water. (3) Mix the t w o solutions together and dilute t o 1000 ml with water. Sulfuric Acid Solution. Carefully add 750 mi of sulfuric acid t o 250 ml of water, cool t o toom temperature, and dilute t o 1000 ml with water. Potassium Bi-iodate Solution N/40. Dissolve -812 g of KH (103) in 1000 ml of water. Sodium Thiosulfate Solution N/40. Dilute 250 ml of standard N /10 Na ,S 20 to 1000-ml with water. (2) Sampling: One 250-ml and one 500-ml Erlenmeyer flask equipped with three-hole rubber stoppers are required. Fit the stoppers with glass tubing so that the inlet tubes reach nearly

104

PART I1 THE ANALYSIS OF INDUSTRIAL WATERS

to the bottom of the flasks; the outlet tubes should be flush with the bottom of the rubber stoppers so that air will not be trapped. Con-

nect the outlet tube of the 500-ml flask to the inlet tube of the 250ml flask and close the third hole in each stopper with a glass plug. Draw the sample by connecting the inlet tube of the 500-ml flask to the sampling valve with rubber tubing and allowing the water to flow through the flasks for at least 30 minutes. Remove the connection to the sampling valve and close the flasks by slipping the rubber tubing connections of the inlet tubes onto the outlet tubes of each flask without trapping any air. PROCEDURE

1. Add to both flasks the following reagents in the indicated sequence using a separate pipet for each reagent: 2 ml of manganous sulfate reagent, 2 ml of alkaline potassium iodide reagent, and, after the floc has settled, 2 ml of sulfuric acid solution. Add the reagents through the holes stoppered with the glass plugs and mix thoroughly after each addition. 2. Transfer the contents of the 500-ml flask to a large porcelain evaporating dish and add 2 ml of starch solution. If the solution does not turn blue, add N/40 potassium bi-iodate solution from a buret until a blue color appears, then add 3 ml in excess. 3. Titrate with standard N/40 NazSzOs solution until the blue color disappears and record the titration as A. 4. Transfer the contents of the 250-ml flask to a similar dish, dilute to about 500 ml with water, and add 2 ml of starch solution. 5. Add exactly the same amount of N/40 KH(IOs)z solution* as added to the 500-ml sample and titrate as above, recording this titration as 8. 6. If titration A is greater than 6, oxygen is present; if B is greater than A, sulfite is present:
ppm O,=(A-B)

x0.8

or, in general,
ppm

OzP

(A-B) x N x 8 x 1 0 6 ml sample x i 0 3

As the same amount of KH(I0,) standard.

solution is added to both samples, it need not be

B. DISSOLVED GASES
ppm N a 2 S 0 3 = ( B - A ) x6.3

105

or, in general,
(6-A) x N x 6 3 x 1 0 6 ppm Na ZSo 3 = - 7 1 c D m 3 -