SECTION 24

METHODS FOR DETERMINATION

OF WATER IN GASES, LIQUIDS
AND SOLIDS
Table 24.1 Methods for the Determination of Water in Gases 24.2
Table 24.2 Methods for the Determination of Water in Liquids 24.4
Table 24.3 Methods for the Determination of Water in Solids 24.7

There is no single technique applicable to measure water in solid, liquid, and gaseous substances
although the Karl Fischer titrimetric procedure is widely used and the method to which all other
methods are often compared. The analytical chemist must review need with respect to required pre-
cision and accuracy, water concentration, and skills available, as well as equipment on hand. Often
speed is the most important criterion, particularly in production facilities. An excellent treatise on
methods for the determination of water is the three-part monograph by Mitchell and Smith.1 There
is also a much abbreviated treatment by Mitchell.2
Selected methods and techniques are outlined in Tables 24.1 through 24.3. Some comments on
various methods are now given.
The Karl Fischer method is perhaps the most widely used procedure for the determination of
water. Although this method works well in many cases, the commercial reagents are rather costly,
the visual titration end point is difficult to discern, and there are numerous interferences, including
oxidizing agents, unsaturated compounds, and thio compounds. Liang3 discusses automatic on-line
monitoring by flow-injection sampling.
Infrared spectrometry is broadly useful for determining water in the gas, liquid, or solid phase.
Several absorption bands can be used; the most useful are located in the near-infrared region at about
1.9 mm and in the fundamental region at about 2.7 and 6 mm. The reviews by Kaye4 and Wheeler5 and
the report by Keyworth6 provide useful information on the near-infrared region.
Procedures based on colorimetry usually employ CoCl2 (blue when anhydrous) or CoBr2 (green
when anhydrous) that change to red for the fully hydrated salts. Cobalt chloride in ethanol gives an
absorption maximum at 671 nm. Anhydrous ethanol can be used to extract water from the solid sam-
ple. Other substances that have found specific uses as colorimetric reagents have been methylene
blue for traces of water in jet fuels, halides, ketones, and hydrocarbons; cobalt bromide–impregnated
strips for testing halogenated refrigerants, gasoline, and oils; fuchsine for estimating water in gran-
ulated sugar and refinery pastes; and chloranilic acid for organic solvents except those containing
amino-nitrogen.

1 John Mitchell, Jr., and D. M. Smith, Aquametry, 2d ed., Wiley, New York, 1977–1980, Parts I–III.
2 J. Mitchell, Jr., in F. J. Welcher, ed., Standard Methods of Chemical Analysis, 6th ed., Van Nostrand, New York, 1966,
Vol. 3, Part B, Chap. 64.
3 Y. Y. Liang, Anal. Chem. 62:2504 (1990).
4 W. Kaye, Spectrochim. Acta 6:257 (1954); 7:181 (1955).
5 O. H. Wheeler, Chem. Rev. 59:629 (1959).
6 D. A. Keyworth, Talanta 8:461 (1961).

24.1
24.2
TABLE 24.1 Methods for the Determination of Water in Gases
Method and technique
Karl Fischer (volumetric)
Succinyl chloride (volumetric)
Magnesium nitride (volumetric)
Cobalt(II) chloride (colorimetric)
Calcium carbide (colorimetric)
Absorption (gravimetric)
Infrared spectrophotometry
Vacuum ultraviolet
Mass spectrometry
Gas chromatography
Thermal conductivity
Mass spectrometry (indirect)
Calcium hydride (thermometric)
Magnesium nitride (conductometric)
Procedure and references Range Interferences
Condensation; alcohol, acid, or tert-amine extraction; titration to electrometric ppm to several per- RCHO, RSH
or visual end point [1]. H2O ≡≡ I2. cent
Pass gas through molten reagent at 60°C, absorb released HCl in water, and 0.1% to few percent ROH, RNH2, R2NH,
titrate with standard Na borate [3]. H2O ≡≡ 2HCl. acids
Pass through reagent at 100°C, absorb NH3 in standard H2SO4 [2]. 0.5% to few percent Other volatile bases
NH3 ≡≡ 3H2O. or acids
Alcoholic extraction; measure absorbance at 671 nm [4]. 0.5% to several Colored substances
percent
Pass gas through CaC2 at 180 to 200°C; pass C2H2 released through ammonia- 0.1%–1% ROH
cal Cu2SO4 and determine as red-colored CuC2 [2,16].
Pass through tared tube containing P2O5 or other suitable desiccant. Increase in ppm Other substances
weight is proportional to H2O [2]. absorbed by desic-
cant
Measure absorbance at suitable wavelength [2,5]. ppm ROH, RNH2
Absorbance of moisture in air at 27.97 mm using a water vapor laser [13]. Other components of air
have negligible effect
Measure absorbance at 127 nm [6]. Low ppm Substances absorbing
105–150 nm, such as
CH4, H2S
Measure m/e = 18 [2]. 0.5%–5% Other compounds con-
tributing to m/e = 18
Separation through packed column of Carbowax 20M or Porapak Q at 150°C 0.5%–5% Other compounds with
[2,7,12]. same retention time
Reaction of H2O with CaC2; separation of resulting C2H2 by gas–liquid (OV-11 ppm to few percent Other compounds with
or DC 710) or gas–solid (silica gel at 80°C) chromatography [2]. same retention time
Separation through packed column of Porapak N [17]. 2–100 ppm
Measure heat transfer [8]. Several volume Hydrocarbons
percent
Pass gas sample through a cold trap containing CaC2 on which water is con- ≥1 mg
densed; heat trap to 90°C and determine C2H2 produced [14].
Measure temperature before and after passage of gas through CaH2 [2]. ppm ROH, RCOCH3,
RCHO, NH3
Absorbed the released NH3 in H3BO3 and measure electrical conductivity [9]. High ppm Other volatile bases
or acids
 Electrolysis Pass through electrolyte cell containing P2O5 and measure current [10]. 1 ppm to 0.1% ROH, RCHO, NH3,
CH3COCH3, HF
Hygrometry Measure relative humidity with psychrometer or hygrometer [2,11]. Several volume
percent
Supersaturation hygrometer utilizing a thermo-optical system that senses Area of 100% rela-
growth of salt particles optically and controls their growth by heating the tive humidity
substrate with an infrared source. Output of heater is a measure of ambient
relative humidity [15].
Dew-point measurement Pass over cooled polished metal surface; measure temperature at which dew 1–1000 ppm Other compounds that
forms, as observed photometrically or visually [2,18]. condense
Vapor pressure (manometric) Measure pressure before and after removal of H2O [2]. Low percent Other substances that
condense
1. J. Mitchell, Jr., and D. M. Smith, Aquametry, 2d ed., Wiley-Interscience, New York, 1977–1980, three volumes.
2. J. Mitchell, Jr., in I. M. Kolthoff and P. J. Elving, eds, Treatise in Analytical Chemistry, Part II, Vol. 1, Interscience, New York, 1961.
3. C. B. Belcher, Thompson, and T. S. West, Anal. Chim. Acta, 19:148 (1958).
4. Singliar and Zubák, Chem. prumysl 6:426 (1956).
5. Curcio and Petty, J. Opt. Soc. Am. 41:302 (1951).
6. Garton, Webb, and Wildy, J. Sci. Instrum. 34:496 (1957).
7. S. Dal Nogare and Safranski, in J. Mitchell et al., eds., Organic Analysis, Interscience, New York, 1960, Vol. 4.
8. R. H. Cherry, Anal. Chem. 20:958 (1948).
9. Peck, Zedek, and Wittova, Chem. prumysl 5:219 (1955).
10. F. A. Keidel, Anal. Chem. 31:2043 (1959).
11. Weaver, Hughes, and Diniak, J. Res. Natl. Bur. Stand. (U.S.) 60:489 (1958).
12. V. M. Sakharov, G. S. Beskova, and A. I. Butusova, Zh. Anal. Khim. 31:250 (1976) (English, p. 214).
13. P. B. Lund and L. Kinnunen, J. Phys. E. Sci. Instrum. 9:528 (1976).
14. G. L. Carlson and W. R. Morgan, Appl. Spectrosc. 31:48 (1977).
15. H. Gerber, Res. Dev. 28:17 (Nov. 1977).
16. W. Boller, Chemiker-Ztg. 50:537 (1983).
17. F. F. Andrawes, Anal. Chem. 55:1869 (1983).
18. E. Flaherty, C. Herold, and D. Murray, Anal. Chem. 58:1903 (1986).
24.3
24.4
TABLE 24.2 Methods for the Determination of Water in Liquids

Method and technique Procedure and references Range Interferences

Karl Fischer (volumetric) Titration in inert solvent (e.g., MeOH or pyridine) to electrometric or visual end ppm to 100% RCHO, RSH, NH2OH,
point [1,2]. (RCOO)2, quinone,
ascorbic acid
Karl Fischer (flow injection) Water in organic solvents determined by flow injection and measurement at 0.001%–0.1% Ketals
546 nm [21].
Acetyl chloride (volumetric) Reaction with reagent at room temperature, treatment of excess reagent with 0.02% to several HCOOH, RCHO,
MeOH, and titration of sample and blank with standard base [1,2]. percent strong R3N, high
concentrations of
ROH, RNH2 or
R2NH
Magnesium nitride (volumetric) After reaction with reagent in Kjeldahl assembly, remove NH3 by steam distilla- 0.05% to several Steam-distillable bases
tion and determine acidimetrically [2]. percent or acids; high con-
centrations of
MeOH
Acetic anhydride (volumetric) Hydrolyze with strong acid and catalyst. Titrate sample and blank with standard 0.1% to several Same as acetyl chlo-
NaOMe [3]. percent ride method
After hydrolysis, add known excess aniline, and titrate sample and blank with 0.1% to several Same as acetyl chlo-
standard HClO4 in HOAc [4]. percent ride method
(conductometric) Titrate sample with acetic anhydride in HOAc, using strong acid as catalyst [2]. 0.01% to few ROH, RNH2, R2NH
percent
(spectrophotometric) Hydrolyze at 110°C and determine excess acetic anhydride by measuring 0.01% to few ROH, RNH2, R2NH
absorbance at 252 nm [2,5]. percent
Infrared spectrophotometry Measure absorbance in near-infrared region, 14 286 to 5000 cm−1 [2]. 0.1% to several ROH, RNH2
percent
Measure absorbance in fundamental region at or near 3590 cm−1. A drying tech- ppm to few percent ROH, RNH2
nique was established employing vacuum distillation onto 4A molecular
sieves [14].
Nuclear magnetic resonance Measure proton resonance. Chemical shift varies with water concentration and Several percent
spectroscopy H bonding [2].
Paper chromatography Measure intensity of blue color from water absorption in paper impregnated 0.1% to few percent
with FeSO4 and K ferricyanide [6].
 Gas chromatography
HPLC
Size exclusion and adsorption
chromatography
Voltammetric sensor
Voltammetry
Acetic anhydride (thermometric)
Distillation
Dielectric constant
Conductivity
Conductometric titration
Calcium carbide (manometric)
Calcium hydride (gasometric)
Luminescence lifetime
24.5
Column packed with Porapak Q and kept at 150°C. 0.03%–2%
Reaction with 2,2-dimethoxypropane and a solid acid catalyst (Nafion resin) for As low as 0.001%
5 min, followed by capillary column GC for acetone formed [16]. or 13.4 ppm
Instantaneous reaction with a 0.5 nM ortho ester (triethyl orthoformate) and cat- As low as 0.001%
alyst (methanesulfonic acid) followed by capillary column GC for ethanol or 13.4 ppm
formed [17].
Columns using microparticulate normal phase, reversed phase, and ion 2.5 ppm up to 50%
exchange with NaCl in eluant and using a conductivity detector [22].
Water and alcohols in gasoline blends separated on HPLC ion exclusion 0.04–0.2 mL
columns (Ultrastyragel 100 and 500 Å) with toluene as mobile phase [20].
Thin-film perfluorosulfonate ionomer sensors overcoated with cellulose triac-
etate, polyvinyl alcohol–H3PO4 composite films operated in a pulsed voltam-
metric mode. Water in sample equilibrates with sensing film between pulses
and is then electrolyzed by the pulse [17].
Molten salt (AlCl3–N-butylpyridinium chloride) and water generates HCl which Linear up to 50 mM
is electrochemically reduced at a rotating Pt disk electrode [19].
Measure temperature rise on mixing sample with acetic anhydride and HClO4 0.5% to few percent ROH, RNH2, R2NH
catalyst [7].
Use a preliminary distillation step with a low-efficiency column, heating up to
135–150°C, then cooling the two-phase distillate at −10 to −20°C. The water
will solidify and reject the dissolved hydrocarbons from the crystal matrix,
which can then be decanted [12].
Measure dielectric constant directly in solution using high-frequency technique 1% to high percent Other compounds
[8]. A microwave resonance method for water in oil emulsions uses the dif- having high dielec-
ference in dielectric properties between water and oil [15]. tric constant
Measure current flowing through electrodes at fixed potential [9]. 0.3% to several Other conducting
percent substances
Titrant is LiH in dimethylsulfoxide for water in organic solvents [11].
Measure pressure rise when sample and CaC2 react in closed vessel [2]. Several percent ROH
Measure volume H2 evolved when sample and CaH2 react in gas-volumetric Several percent ROH, RCHO, NH3
apparatus [9].
Water in dimethylformamide and dimethylsulfoxide determined by lumines- 0.05–5 mol %
cence lifetime measurements of Eu(III) [18].
(Continued)
24.6
TABLE 24.2 Methods for the Determination of Water in Liquids (Continued)

Method and technique Procedure and references Range Interferences

Turbidity Measure turbidity or cloud point on titration with water-immiscible liquid (e.g., 0.3% to few percent Other compounds only
xylene or mineral oil) [2]. slightly soluble in sample
solution
Density or specific gravity Measure specific gravity directly in known system where water is only variable [2]. Variable Unknown constituents
Refractometry Measure refractive index of known system where water is only variable [2]. Variable Unknown constituents
Radiochemical (b -ray absorp- b -Rays passed through sample and measured with appropriate counter [10]. 0.1%–1% ROH
tion)
1. J. Mitchell, Jr., and D. M. Smith, Aquametry, 2d ed., Wiley-Interscience, New York, 1977–1980, in three parts.
2. J. Mitchell, Jr., in I. M. Kolthoff and P. J. Elving, eds., Treatise on Analytical Chemistry, Interscience, New York, 1961, Part II, Vol. 1.
3. Toennies and Elliott, J. Am. Chem. Soc., 57:2136 (1935); 59:902 (1967).
4. Das, J. Indian Chem. Soc. 34:247 (1957).
5. S. Bruckenstein, Anal. Chem. 28:1920 (1956).
6. Stringer, Nature, 167:1071 (1951).
7. L. H. Greathouse, H. J. Janssen, and C. H. Haydel, Anal. Chem. 28:356 (1956).
8. Oehme, Angew. Chem. 68:457 (1956).
9. Perryman, Analyst 70:45 (1945).
10. Friedman, Zisman, and Sullivan, U.S. Patent No. 2,487,797 (1949).
11. C. Yoshimura, K. Miyamoto, and K. Tamura, Bunseki Kagaku 27:310 (1978); Chem. Abstr. 89: 16126 (1978).
12. T. H. Gouw, Anal. Chem. 49:1887 (1977).
13. J. Kovarik, Chem. Abstr. 86:56052 (1977).
14. A. Barbetta and W. Edgell, Appl. Spectrosc. 32:93 (1978).
15. D. A. Doherty, Anal. Chem. 49:690 (1977).
16. K. D. Dix, P. A. Sakkinen, and J. S. Fritz, Anal. Chem. 61:1325 (1989).
17. H. Huang and P. K. Dasgupta, Anal. Chem. 64:2406 (1992).
18. S. Lis and G. R. Choppin, Anal. Chem. 63:2542 (1991).
19. S. Sakami and R. A. Osteryoung, Anal. Chem. 55:1970 (1983).
20. M. Zinbo, Anal. Chem. 56:244 (1984).
21. I. Norden-Andersson and A. Edergren, Anal. Chem. 57:2571 (1985).
22. T. S. Stevens and K. M. Chritz, Anal. Chem. 59:1716 (1971).
 TABLE 24.3 Methods for the Determination of Water in Solids
Method and technique
Karl Fischer (volumetric)
Oven drying (gravimetric)
Thermogravimetry
Thermogravimetry and differ-
ential thermal analysis
Desiccation (gravimetric)
Microwave drying (gravimetric)
Freeze drying (gravimetric)
Calcium carbide (gravimetric)
Infrared spectrophotometry
24.7
Procedure and references Range Interferences
Extraction with, or solution in, an inert liquid (MeOH, pyridine, CHCl3, or 0.01% to high MOH, MO, MCO3, Cu(II),
1,4-dioxane) [1,2]. percent FeCl3, NH2OH, borates
Heat sample to constant weight at ≥100°C at 1 atm or ≤100°C at <1 atm [2]. 0.1% to high Other volatiles, thermally
percent unstable materials,
incompletely dehydrated
hydrates
Measure weight loss as function of time and temperature [2]. Few to several See above
percent
At ambient to 250°C results for grains were same whether made in static or
flowing air or N2 at atmospheric or reduced pressure [10].
Dry sample at room temperature at ≤1 atm; absorb water with P2O5 or 0.1% to high Other volatile materials
Mg(ClO4)2 and determine loss in weight of sample or gain in weight of percent
Mg(ClO4)2 [2].
Constant weight loss is obtained in 5 min [9].
Sublimation of water from sample at <0°C in vacuo [3]. Few to several
percent
Add known weight of CaC2 to sample in tared vessel; heat mixture to ca. Several percent Other volatile substances
100°C, cool, weigh. Net loss in weight is equivalent to water [4].
Measure absorbance of iodine samples at 3665 cm−1 and subtract baseline 0.1% to several ROH, RNH2
value at 4000 cm−1 [11]. percent
Reflectance measurements in near-infrared region used for moisture in malt <1%
[12], powdered pharmaceutical products [13], and in clay powders and
flakes [14]. Measure reflectance at 1.93 mm for water and at 1.7 mm
for background.
The integrated absorption of the scissoring vibrations of water at 1640 cm−1
varied linearly with water content of polymer membrane irrespective of the
nature of the cation [15].
Peak height absorbance of band at 5236 mm used for poly(methylmethacrylate)
studies [16].
(Continued)
24.8
TABLE 24.3 Methods for the Determination of Water in Solids (Continued)
Method and technique
NMR spectroscopy
Fluorescent x radiation
Distillation
Dielectric constant
Calcium carbide (manometric)
Vapor pressure (manometric)
Displacement
Radiochemical methods
Procedure and references Range Interferences
Measure proton signal from low-resolution instrument [6]. Few to high Other proton-containing
percent liquids
Measure the extent of attenuation of fluorescent x radiation excited from a Up to 500 g/m2
sheet of iron or copper on which paper is placed [17].
Separate water by azeotropic distillation at ≤1 atm [2]. 0.1% to several Other volatile water-
percent miscible substances
Measure dielectric constant of sample or extract with 1,4-dioxane [2]. Few to several Other substances having
percent high dielectric constants
Treat sample with CaC2 in pressure flask; measure increase in pressure. Several percent Other substances reacting
with CaC2
Evacuate closed system containing sample, then heat sample and collect water 0.1% to few Other volatile substances
vapor in manometer [2]. percent
To known weight of wet sample, add known volume of water in graduated High percent Other liquids
vessel; measure total volume and correct for volumes of dry solid and water
added.
Pass g radiation from source (e.g., Cs-137) through sample; detect by High percent
ionization chamber [2].
Irradiate a powdered sample in a neutron flux of about 4.8 × 107 n ⋅ cm−2 ⋅ s−1;
resulting H g radiation is measured at 2.232 MeV and that from the TiO2
internal standard at 1.381 MeV [18].
Sample of ion exchange resin is mixed with tritium-labeled water of known ≥0.1 pg or <0.5%
activity and extracted with dry 1,4-dioxane in a Soxhlet apparatus. Residual water
3HHO activity measured following addition of weight amount of inactive
H2O. Activity of solution is measured after reducing 3HHO to 3HH with Zn
amalgam and counting the gas [19].
Hydrogen is more capable than other elements of slowing and scattering fast Several percent Other substances
neutrons (Po–Be source); used to determine moisture in soils [21]. containing hydrogen
 Conductivity (relative) 300–500-mg glass sample is heated with 500–800 mg of CuO at 1250°C in a 20–500 mg
tube furnace; released water is carried by N2 stream over Ag wool and into
cell containing PCl5 to form POCl3 (retained in cold trap) and HCl which is
absorbed in 14 mM HCl. Relative conductivity measured [20].
1. J. Mitchell, Jr., and D. M. Smith, Aquametry, 2d ed., Wiley-Interscience, New York, 1977–1980, in three parts.
2. J. Mitchell, Jr., in I. M. Kolthoff and P. J. Elving, eds., Treatise on Analytical Chemistry, Interscience, New York, 1961, Part II, Vol. 1.
3. B. Makower and E. Nielsen, Anal. Chem. 20:856 (1948).
4. Williams, McComb, and Washauer, Food Ind. 22:458 (1950).
5. L. Shapiro and W. W. Brannock, Anal. Chem. 27:560 (1955).
6. Shaw and Elsken, J. Assoc. Offic. Anal. Chem. 36:1070 (1953).
7. Martin and Mounfield, U.S. Patent No. 2,874,564 (1959).
8. Serger, Chemiker-Ztg. 78:681 (1954).
9. S. Yamaguchi, M. Kubo, and K. Konishi, J. Am. Oil Chem. Soc. 54:539 (1977).
10. M. B. Neher, R. W. Pheil, and C. A. Watson, Cereal Chem. 50:617 (1973).
11. R. N. P. Farrow and A. G. Hill, Analyst 102:480 (1977).
12. M. Moll, R. Flayeux, and J-M. Leheude, Bios (France) 7:3 (1976).
13. H. Seager, J. Burt, and H. Fisher, J. Pharm. Pharmacol. 1976:28, Suppl. 62P.
14. G. Vondracek, Ber. Dt. Keram. Ges. 52:185 (1975).
15. L. Levy, H. D. Hurwitz, and A. Jenard, Anal. Chim. Acta 88:377 (1977).
16. A. S. Gilbert, R. A. Pethrick, and D. W. Phillips, J. Appl. Polymer Sci. 21:319 (1977).
17. S. Aksela, Paperi Puu 57[4a]:183, 187 (1975); Chem. Abstr. 31[1]:1C55 (1976).
18. M. Heurtebise and J. A. Lubkowitz, Anal. Chem. 48:2143 (1976).
19. E. Blasius and R. Schmitt, Z. Anal. Chem. 241:4 (1968).
20. H. Malissa, E. Pell, and H. Puxbaum, Z. Anal. Chem. 278:353 (1976).
21. Gardner and Kirkham, Soil Sci. 73:391 (1952).
24.9