Table I. Kinetic resuits on Ethyl Acetate Thermolysis Temperature E log A range (sec.-,) (kcal. mole ') lit.

ref. (G)
-

12.6 12.6 12.8 12.1 12.4 12.5 454-519 a) log A calculated theoretically b) pulse injection technique c) continuous flow of reactant 500-603 386-487

48.2 48.0 48.3 46.4 47.6 47.6

9a 10 5 4b 4 this work

plug- and tank-flow behaviour, o log k I (Figure 3) should be a simple function of the percentage of decomposition (order of magnitude for type C reactors: for 10% decomposition Alog k i = 0.01; 50% dec., Jog k x - 0.10) . Uncertainties introduced by this way of calculation will be small as compared with experimental errors (e.g. wall effects, side reactions, temperature measurement) . Kinetic data on the standard reaction, n-butyl acetate thermolysis, obtained by different operators in different type C units, showed a good reproducibility: E = 47.3 0.5 kcal mole '; log A (sec-2
-

) = 12.1 0.2

Arrhenius parameters for ethyl acetate thermolysis are n well in accord with literature data (Table I). Manuscript received February 5, 1970.

plug-flow/tank-flow rate "constants" can be derived (5): kipt/kltf = [Ec/ (Eo - E t 1n E,/E t
) ]

Thus, assuming that the intermediate type of flow in our system can be treated as a linear combination of

9. O'Neal, H. E., and Benson, S. W., J. Phys. Chem, 71, 2903 (1967). 10. Blades, A. T., and Gilderson, P. W., Can. J. Chem. 38, 1407 (1960).

Gas Chromatographic Analysis of Trace Contaminants in Liquid Ammonia

by Raymond F. Mindrup, Jr. and John H. Taylor,* Engineering Laboratories, McDonnell Aircraft Company, St. Louis, Missouri 63166

Abstract
The need for high-purity liquid ammonia prompted the investigation of methods of analysis of ammonia for water and for contaminants not condensible at the liquefaction temperature of ammonia. GC methods were investigated for the analysis of traces of 0 2 , N 2, CO, CO 2, CH 4 and H 2 0 and detection limits of better than 3 ppm were attained for the gaseous contaminants. Techniques for overcoming ammonia tailng are described, and the effect of ammonia on column

The distillation-and-measurement-of-residue method (1) is limited in accuracy below 100 ppm concentration. The dew point method (2,3) is limited in accuracy due to undefined interactions, and the coulometric method (4) is not applicable to routine determinations. Indirect methods of analysis of water as a contaminant (5-8) are time consuming and subject to

life is considered. Sampling problems encountered with liquid ammonia are described, and a special sampling arrangement is presented. Chromatograms, which were obtained by employing the columns and conditions which produced the maximum sensitivity and necessary resolution, are presented.

*Present Address: Martin Marietta Corporation, Denver, Colorado 80201.

Introduction
Liquid anhydrous ammonia is used extensively as a coolant in heat exchange systems because of its chemical stability, low corrosiveness, and high latent heat of vaporization. Anhydrous ammonia, however, is readily contaminated during handling and storage and must be purified before use. To verify that purification has been achieved, a rapid and direct method of analysis for trace contaminants is needed. A review of analytical methods revealed that the conventional methods are inadequate for the analysis of trace concentrations of water in liquid ammonia.
JOURNAL OF CHROMATOGRAPHIC SCIENCE VOL 8

1. Anon., Ammonia Technical, Federal Specifications O-A-445a, U.S. Government Printing Office, Washington, D.G., January 31, 1961. 2. Anon. Standard Method of Test for Water Vapor Content of Gaseous Fuels of Measurement of Dew Point Temperature, D1142-63, ASTM Standards, Part 19, p. 237 - 49, American Society for Testing and Materials, Philadelphia, Pa., 1964. 3. Weyler, Arnold, and Brombacker, W. G., N.B.S. Arula No. 512, Methods of Measuring Humidity and Testing Hygrometers, September 1951. 4. Klingelhoefer, W. C., Anal. Chem. 34, 1751 (1962). 5. Guenant, G. 0., Anal. Chem. 39, 142 (1967). 6. Duswalt, A. C., and Brandt, W. W., Anal Chem. 32, 272 (1960). 7. Linde, H. W., and Rogers, L. B., Anal. Chem. 30, 1250 (1958). 8. Sundberg, O. E., and Maresh, Charles, Anal. Chem. 32, 274 (1960).

DECEMBER 1970 723

Table 1. Experimental Parameters

Analysis of 0 2 , N 2 , CH, and CO Column 6 ft x 1/4 in., o.d., 0.028 in. gage stainless steel: MoIecular Sieve 5A, 80/100 Mesh Thermal Conductivity: Thermistor at 15 ma
60C

Analysis df H 2 O

Analysis of CO

Detector Temperature Column Detector Injector Flow Rate Recorder

/s in., o.d. 0.028in. gage stainless steel: 8 ft 18 ft x 1 Porapak R, 80/100 Mesh; and 10 ft Porapak R, 80/100 Mesh, with 10% Polyethylenimine (PEI) Thermal Conductivity: Thermal Conductivity: Thermistor at 15 ma Thermistor at 15 ma
80C 60C

Ambient
60C

50 ml/min 0.5 in./min

Ambient 80C 70 ml/min 0.5 in./min

Ambient
60C

50 mi/min 0.5 in./min

error in the conversion of water to the analyzed product and the Karl Fischer method is not applicable due to the interaction between ammonia and the reagent. An array of standard methods is available which can be used to analyze the gaseous contaminants; these include Orsat absorption, total hydrocarbon combustion, and application of the magnetic field effect. Howover, GC analysis would be preferred since it offers speed, simplicity, sensitivity, and specificity, if the effects from the ammonia medium could be eliminated. Therefore, a method was developed to analyze liquid ammonia by direct sampling of the ammonia gas into the gas chromatograph. Inert polymer beads were used as a column packing to separate water and carbon dioxide from the ammonia and to eliminate the tailing effect of ammonia. The noncondensible gas contaminants, 0 2 , N 2 , CH 4 and CO, were analyzed by using a Molecular Sieve 5A column, which absorbs the ammonia.

Figure 1. Sample container.

Experimenta1
The GC used in this work was an F&M Research Model 5750 equipped with a gas sampling valve and a Carle microcavity thermistor detector. Two columns were used for analysis of the contaminants in liquid ammonia, and the instrument parameters for both columns are presented in Table I. Both columns were constructed of 0.028 in. gage, stainless steel tubing and coiled to fit the internal connections of the gas chromatograph. These columns were prepared in the laboratory with the exception of the section containing Porapak R (Waters Assoc., Framingham, Mass.) with polyethylenimine, PEI, which was purchased from Varian-Aerograph. These columns were conditioned for a minimum period of 12 hours at a temperature of 180C and a 30 ml/min heilum flowrate, except for the molecular sieve which was conditioned at 250C.

Procedure
The liquid ammonia and standard gases were sampled directly by using a gas sampling valve. Varia724 DECEMBER 1970

tions in contaminant concentrations in the liquid ammonia and in the vapor above the liquid ammonia were investigated by sampling with the sample container in an inverted and upright position, respectively. (Figure 1 illustrates the containers in both modes of sampling), In the inverted position, a 10 in. long x 1/8 in., o.d., loop of 0.028 in gage stainless steel tubing was attached to the sample container for vaporizing the liquid ammonia prior to sampling. The connecting Tines, gas sampling valve, columns, and sample containers were constructed of stainless steel to prevent any interactions of the ammonia with these parts. The flowrate of the gaseous ammonia sample was monitored at the exit port of the gas sampling valve and accurately controlled to provide repeatable analytical conditions. Interactions between the ammonia and the contaminants were investigated by adding to the liquid ammonia a measured amount of each contaminant and determining the amount of contaminant recovered in the subsequent analysis. The effect of ammonia gas on the life of the detector and columns was investigated by comparing the response, noise, and resolution of standards before and after repeated injections of ammonia gas into the columns.
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Resuits and Discussion Tailing and resolution problems were encountered in the analysis of trace amounts of water in liquid ammonia. To eliminate these problems, several column configurations were investigated. First, the ammonia was passed through a combination of one 8 ft length of Porapak Q and one 8 ft length of Porapak R connected to form a 16 ft column. This column was successfully used to separate low concentrations of both ammonia and water (9), but it was not effective in eliminating the tailing in trace analysis of water in high concentrations of ammonia, as shown in Figure 2. Next, an evaluation of silanized Porapaks P-S and Q-S indicated that both were inadequate in separating trace amounts of water from ammonia; although the tailing effect was minimized, resolution was not complete. The final configuration, a combination of 8 ft of Porapak R with 10 ft of Porapak R coated with 10% PEI (10), resulted in adequate separation of water from ammonia with no tailing of ammonia at the elution of the water peak, as shown in Figure 3. The combination also allowed the use of a high flowrate and a low column temperature. Water concentrations of 5 ppm were detectable in the liquid ammonia samples. In an effort to improve the analysis for trace quantities of water in liquid ammonia by increasing the water concentration, the ammonia was evaporated at am-

25C

0C

15C

x 160

24 26 Time - Minurn

Figure 4. Ammonia head gas sampling.

A. UPIUGGT PGSITIGG GASEWS SIIDPUIIG

5160

x2

x2

02

x2

X4

D. IDIIEIITED PDSITIGG

uquw SADPl1DD

Figure 5. Water concentration distribution.

Time Mi

Figure 2. Incomplete resolution of ammonia and water.

Al,

NH3 H20

E
G

bient temperature, 0C, and 15C. The ammonia head gas was sampled at each temperature and, as shown in Figure 4, only minor changes occurred in the water concentration as the temperature was lowered. Also, the ammonia was allowed to evaporate entirely at ambient temperature and was sampled alternately as head gas and liquid during the evaporation. Figure 5 illustrates the changes in water concentration of both states of ammonia. The water concentration in the liquid state is notably more reproducible but shows a much lower concentration than in the head gas. The increase in water concentration as the sample is depleted is attributed to completion of ammonia evaporation. This investigation indicates the need for sampling ammonia as a liquid rather than as head gas. Concentration of the noncondensible contaminants, 0 2 , N 2 , CH 4 and CO, were determined using the 6 ft Molecular Sieve 5A column, and CO 2 was analyzed using the two Porapak R columns. Because ammonia gas is absorbed by the molecular sieve, contaminants are resolved without the tailing effect of ammonia. The four noncondensible contaminants were readily re-

X 800
X4

18 8 Time Minutes

20

22

9. Wilhite, W. F., and Hollis, 0. L., J. Gas Chromatog. 2, 84 (1968). 10. Hollis, O. L., Anal. Chem. 38, 309 (1966).

Figure 3. Resolution of ammonia and water JOURNAL OF CHROMATOGRAPHIC SCIENCE VOL 8 DECEMBER 1970 725

solved at 60C. Figures 6 and 7 show the noncondensibie contaminants resolved in a standard gas mixture 25OPP' in helium and in trace concentrations in an ammonia sample. A detection limit of better than 3 ppm was attained for the four contaminants. The carbon dioxide determination was achieved on the two Porapak R columns prior to the elution of ammonia. The column temperature was decreased to 60C and the flowrate was reduced to 50 mi/min to obtain adequate resolution. The carbon dioxide eluted 0.5 minute prior to the ammonia and a detection limit of better than 10 ppm was obtained. In the course of the analyses interactions of ammonia with the noncondensible contaminants were investigated by adding contaminants to ammonia. Anhydrous ammonia gas was first condensed into a pre cooled 75 mi stainless steel container, and the quantity of liquid ammonia was determined by weight difference. The liquid ammonia was then allowed to expand into a 4 liter stainless steel container which had proviously been evacuated and then had known quantities of the gaseous contaminants introcluced. Concentrations of the contaminants were in the 100 ppm range. The ammonia was then analyzed as previousiy described, and the recovery of each contaminant was better than 95%. Since no interactions were noted between the ammonia and contaminants, standard gas mixtures in nitrogen and helium were used for all subsequent analyses. To determine the extent to which water could be recovered from the sample, known quantities of water were added to cooled liquid ammonia which was subsequently analyzed in both the liquid and gaseous forma. The water concentrations during the analyses of the two phases showed the same distribution as that previonsly deseribed. The effect of ammonia on the life of the molecular sieve column was also studied. Samples of air were used to indicate changes in the resolution of oxygen and nitrogen. After about 400 ml of ammonia gas had passed through the column, an approximate 60% reduction was noted. However, it was possible to recondition the column by heating at 300C for a period of at bast 12 hours with a nominal helium purge. The ammonia did not appear to affect the efficiency of the PEI-coated Porapak R column. The thermistor detector was affected, as indicated by an increase in noise and back of sensitivity. The stainless steel connections and inlet lines to the column, continuously purged with helium between analyses, were not visibly affected.

02

C14

co
285ppm

.5

Figure 6. Standard gas mixture.

LL
47 pp. 02 4 Ti - Mnote*

co

0 .5

Figure 7. Trace concentrations in

5fl

ammonia sample.

ConcIusons
GC methods have been established for the analyses of traces of 02, N 2 , CO, CH 4 , CO, and H 2 0 and detection limits of better than 3 ppm have been attained for the gaseous contaminants. Water concentrations of 5 ppm were detectable in the liquid ammonia.

A comparative study of the liquid and gaseous sampling techniques indicated that the sampling of ammonia as a liquid provided more reproducible resuits. Contaminant concentrations were compared for the vapor and liquid phases of ammonia in the sample container. When sampled as head gas (sample container in an upright position), the contaminant concentrations decreased as the liquid ammonia became depleted; when sampied as a liquid (sample container in an inverted position), the contaminant concentrations were iower than the values obtained from the head gas sampling, but the values were consistent throughout the procedure. This GC method provides sensitive and expedient analysis for trace contaminants in liquid ammonia. Present efforts to increase the sensitivity of this method appear promising. Manuscript received March 4, 1970.

726 DECEMBER 1970

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