Review of Literature 

on Evaporation 

Suppression

By GEORGE B. MAGIN, JR., and LOIS E. RANDALL 

STUDIES OF EVAPORATION

GEOLOGICAL SURVEY PROFESSIONAL PAPER 272-C

UNITED STATES GOVERNMENT PRINTING OFFICE, WASHINGTON : 1960
UNITED STATES DEPARTMENT OF THE INTERIOR 

FRED A. S EATON, Secretary

GEOLOGICAL SURVEY 

Thomas B. Nolan, Director

For sale by the Superintendent of Documents, U.S. Government Printing Office 

Washington 25, D.C. - Price 20 cents (paper cover)
CONTENTS

Page 

Abstract_ ______________._____-______.____--_--__- 53

Introduction. ______-____________-____--____-__----_ 53

Theory of evaporation_____________________________ 53

Studies of factors affecting evaporation________________ 54

Measurement of evaporation.____________--_--__---__ 54

Evaporation suppression___________________________ 55

Techniques in evaporation suppression________________ 56

Bibliography- ______-_______-___---.___--__--------_- 61

in

STUDIES OF EVAPORATION

REVIEW OF LITERATURE ON EVAPORATION SUPPRESSION

By GEORGE B. MAGIN, JR., and Lois E. KANDALL

ABSTRACT

Evaporation suppression is the reduction of evaporation by 

controlling the rate at which water vapor escapes from water 

s -Trf aces. The need for water saving is greatest in areas of little 

iMnfall and low runoff. Water losses by evaporation from storf ~e reservoirs must be minimized for greatest utility of limited 

supplies.

A review of the literature shows that evaporation can be ret^rded by either physical or chemical means. *It can be cont-oiled by enclosure in a building, application of plastic covers, 

< 'I films, and monomolecular films.

Monomolecular films hold the greatest promise for use on large 

i ~eas of water such as reservoirs. From the literature available 

i is apparent that these fibns introduce many chemical and 

physical problems. The suppressants must be nontoxic and 

(-lorless, especially if used on water-supply reservoirs. They 

e v.ould allow the free exchange of oxygen so that aquatic life is 

rot endangered. The effects of water-borne bacteria on these 

f 1ms and the effects of the fibns on water of different qualities 

rre not fully known. The physical problem of detecting the 

presence of the film has not yet been solved. Of the monomolecular films that have been investigated, the waxy alcohols such 

f hexadecanol and octadecanol show the greatest promise.

INTRODUCTION

Maximum use of a short water supply can be obtained 

\j applying conservation methods, such as storing water 

rt times of surplus for use in times of drought. Unfortunately, not all the water put in surface storage is availr ble for future use because part is lost through evaporation. The evaporation loss is serious because it is 

irsually greatest in dry areas where the supply is most 

•valuable. For example, in the Great Basin and the 

Colorado River basin, where the needs for water exceed 

Tie amounts available, evaporation dissipates almost 

c ne-sixth of the available supply (108) .* Great economic gain would result in all arid areas if as much as onefourth of the evaporation from stored water could be 

prevented.

This paper is a brief review of the more significant 

E tudies on the theory and methods of reducing evaporation. The work is part of the studies on evaporation

i Numbers In parentheses refer to references in the bibliography.

suppression by the U.S. Geological Survey. An extensive search of the literature relating to methods of evaporation suppression discloses significant progress to date 

and suggests that more effective methods may be 

developed.

The authors found very helpful the extensive bibliographies of the Southwest Research Institute and of the 

other writers whose names are preceded by asterisks in 

the bibliography. However, some of the references in 

those biblographies were not used as they did not se^m 

pertinent to the subject matter covered here.

THEORY OP EVAPORATION

Four main factors affect evaporation: the area of 

exposed water surface — the larger the area, the greater 

the loss; the temperaturejof the water and air above it — 

a higher temperature increases loss; the movement of 

air above the water surface — a greater movement carries off more vapor; and the relative humidity — dry air 

absorbs moisture more readily than moist air.

According to the kinetic theory of evaporation, na olecules of water are in a constant state of random motion, 

colliding with one another, and rebounding. In the 

liquid state, these molecules are held in balance by tl tit 

cohesive force; however, some molecules possess sufficient kinetic energy to overcome this cohesive force B id 

break free from the water surface, thus forming gaseous 

molecules.

The fundamental law of evaporation is credited to 

Dalton (87). His generalized formula of evaporation 

(88),

was proposed in 1834. In his formula

E =rate of evaporation in inches per day;

Pm= vapor pressure in the film of air next to the

water surface;

PB =± vapor pressure in the air above the film; 

C = coefficient that is dependent upon barometric 

pressure, wind velocity, and other variab1 *^.

53
54 STUDIES OF EVAPORATION

Many investigators since Dalton have contributed to 

the theory and laws of evaporation (see 33, 37, 49, 84, 

86, 89, 120, 124, 154, 180, 188, 190, 207, 227, 236, 281, 

282). Using theoretical considerations and measured 

rates of evaporation of water from plane, cylindrical, and 

spherical surfaces in an air stream, Missenard (212) concluded that evaporation and convection are related and 

are expressed by the same quantitative laws.

STUDIES OF FACTORS AFFECTING EVAPORATION

Evaporation depends on several factors in addition to 

the four previously mentioned. Some investigators 

have considered the effect of barometric pressure and 

solar radiation. Dalton's (87) fundamental derivation 

considered the effect of vapor pressures, wind velocity, 

and barometric pressure. The effect of vapor-pressure 

differences at the air-water interface has been studied by 

Matsak (208) and others (36, 39, 120, 159, 207, 229, 

312). Tzentnershver (304) investigated the effect of 

wind velocity and found that the rate of evaporation of 

water is proportional to the velocity of the air current at 

the water surface, provided that the temperature in the 

surface layer of the liquid is constant. Timofeev (294) 

studied the effects of turbulent air flow. Folse (115) 

concluded that wind velocities less than 10.8 miles per 

hour had no effect on evaporation, but that evaporationpan studies do not seem to support this conclusion.

Stelling (275), in his pan experiments in Russia 

(1875-1882) worked out an approximate formula based 

on wind velocity,

£"=(0.8424+0.01056^) («,-«„)

in metric units, in which E (evaporation) and the difference in vapor pressure (es —ed) are given in millimeters and the wind velocity IF is in meters per second. 

Powell (233),Lur'e and Mikhailov (187), Himus (151), 

and Carrier and Lindsay (71) studied the effects of 

wind velocity and temperature. Himus and Hinchley 

(152) studied the effect of air movement on the rate of 

evaporation of water below the boiling point. Their 

paper cites several references. Many other men have 

studied the effect of wind velocity (31, 32, 76, 85, 98, 

117, 120, 153, 190, 208, 209, 213, 225, 227, 229, 280, 

281, 282, and 312), but to discuss their contributions is 

beyond the scope of this report.

Sharpley and Boelter (266) developed an evaporation 

formula based on the humidity and temperature of 

the water. From water-surface temperature measurements, Alty (37, 38) calculated the maximum rate of 

evaporation. Carrier and Lindsay (71, 72) studied the 

effect of water and air temperature on evaporation. 

Cummings and Richardson (86) applied a correction 

factor for temperature to their thermodynamic equation of evaporation. Others (120, 151, 152, 237, and 

238) have used temperature data in their formulas.

The effect of barometric pressure has been studied by 

Folse (115), Russell (255), and Matsak (208). Quilez 

(238) criticized the existing formulas for calculating 

evaporation from a free surface. He derived an expression that does not involve empirical constants and 

requires the measurements of only air and water temperature and pressure. Other investigators have studied the effects of humidity (85, 86, 207, 266), solar 

radiation (85), altitude (62), surface area (76, 109, 114, 

223, 229, 305), and other factors (148, 149, 154, 306).

Chakravorty (76) studied the evaporation from a free 

surface that was of restricted area and in which shape, 

orientation, and edge effect influenced appreciably the 

overall evaporation.

MEASUREMENT OF EVAPORATION

Evaporation has been determined by several methods. 

Wisler and Brater (319) list five general methods: The 

storage equation, measurements in an auxiliary pan and 

reducing the pan evaporation to natural water surfaces 

by means of a coefficient, the evaporation formula, the 

humidity and wind velocity gradient, and the measurement of insolation.

Other men have taken into account many related 

factors and have proposed different evaporation equations. Fitzgerald (112) modified Dalton's equation by 

taking into account wind velocity,

E= (0.40+0.199W) («,-«<,),

in which PF=wind velocity. Carperter (70) experimented with a sunken tank in 1887. His equation,

#= (0.39+0.187 JF) («,-«„),

is a modification of Fitzgerald's and is applicable to 

conditions in western United States.

Boelter and others (61) worked out curves and equations of evaporation at air temperafrires between 65° 

and 80°F. and relative humidity between 54 and 98 

percent. They list 13 references. Hickox (150) experimented in still air under controlled conditions. He 

drew an analogy between heat transfe" and mass transfer as they occur in evaporation and expressed evaporation rates in terms of appropriate dimensionless groups. 

He considered the effect of vapor-pressure differences, 

wind velocity, pan diameter, water temperature, air 

pressure, rim height, color of pan, and depth of pan. 

His report contains 42 references on evaporation, most 

of which are included in this paper. Others have contributed to our knowledge of measurable factors influencing evaporation (see 76, 114, 115, 151, 180, 184, 187 

255, 266, 275, 306).
REVIEW OF LITEEATUEE ON EVAPORATION SUPPEESSION 55

Thomas and Ferguson (288) reviewed part of the 

literature and pointed out the confusion in terms and 

the variation in formulas developed by different authors 

under different conditions. Livingston (183) published 

an annotated bibliography of evaporation.

EVAPORATION SUPPRESSION

The study of evaporation suppression on large areas 

such as lakes and reservoirs requires a method of evaluating the evaporation that would have occurred during the same period without the suppressant. Comparison of evaporation from two identical reservoirs side 

by side and similarly oriented is one solution; however, 

such reservoirs rarely exist in nature. A more commonly used method is a comparison with nearby evaporation 

pans having concurrent records.

Kohler and others (165, 166) have calculated evaporation from lakes by converting measured evaporation 

from pans to lake evaporation by applying coefficients. 

Kohler and others (166) describe a combination masstransfer and energy-budget approach first suggested by 

Penman (230).

Blaney (57, 58) studied the effects of high altitudes 

on evaporation from pans. He adjusted these data to 

natural lakes and reservoirs by applying a coeffiicient. 

The study was inconclusive because the pans froze during the winter.

Sleight (272) used coefficients to convert pan evaporation to reservoir evaporation. Bonython (62), using 

data from South Australia, demonstrated how errors 

can be introduced into the use of a tank evaporimeter to 

derive evaporation rates from large bodies of water.

Blaney (58) compiled data on evaporation from water 

surfaces in California, and Bloodgood (60) compiled all 

known data on water evaporation in Texas. Bloodgood 

also discussed procedures and coefficients to use in adjusting pan evaporation losses to natural lake or reservoir losses.

Bigelow (55) showed that the location of pans relative to the water of a reservoir has an important effect 

on the calculated evaporation. He concluded that 

water is evaporated from a lake or reservoir about fiveeighths as fast as from an isolated pan placed outside 

the vapor blanket. Kohwer (250, 252) found that the 

evaporation coefficient differs for different types of pans 

and summarized the available records of comparative 

rates of evaporation from different types of pans and 

large bodies of water under similar conditions. He discusses the factors that cause evaporation and the 

derivation of the general law under which these factors 

operate.

Mansfield (191, 192) used a sunken pan to assess 

the effectiveness of evaporation suppressants. This

evaporimeter was calibrated to measure evaporation 

from small ponds that were used in a field test of hexadecanol. Kohler (165) showed that, for a sunken pan 

used in the Lake Hefner study, the monthly coefficient 

used to convert pan evaporation to lake evaporation 

ranged from about 0.2 to 1.5. He concluded that 

Mansfield's evaporimeter may be satisfactory for measuring evaporation from small ponds but may be subject to considerable error if used for large reservoirs.

Harbeck and Koberg (134) conclude that a better 

method of assessing the suppression of evaporation may 

be obtained by using a combination of the ene^gybudget and mass-transfer evaporation measurement 

techniques.

The energy-budget method of measurement was suggested by Angstrom (44) in 1920. It is based on the 

conservation of heat energy within a body. For any 

given body of water a balance must exist between heat 

gains and losses. Heat may be gained by long- and 

short-wave radiation, conduction, and condensation. 

Heat losses result from direct and reflected radiation, 

conduction, advection, and evaporation. Radiation, 

conduction, advection, and changes in energy storage 

in the water may be measured, and the evaporation or 

condensation may be computed.

Bowen (64) determined that the ratio of heat losses 

by conduction and by evaporation from any water 

surface is

#=0.46 (T.-TJ P 

(P.-PJ. 760

where R is the Bowen ratio, and Ta and Pa are the 

original temperature and vapor pressure of the air 

passing over the lake, and Tw and Pw are the corresponding quantities for the layer of air in contact with 

the water surface.

Cummings and Richardson (86) use the Bowen ratio 

in their equation,

(H-S-O

which takes into consideration the net radiant energy 

absorbed and the heat stored in the water. In their 

equation, E is the evaporation, H the difference between the incoming and outgoing radiation, S the heat 

stored in a column of water having unit cross section, 

C a correction for heat carried by flowing water and 

leakage of heat through the walls of the vessel, L the 

latent heat of water, and R the Bowen ratio.

UNESCO (306) published an equation of the thermal 

balance at the evaporating surface as

R^LE+H+G
56 STUDIES OF EVAPORATION

where jR=net radiative flux at evaporating surface, 

L= latent heat of evaporation of water, 

.Z?=rate of evaporation per unit area, 

H=rate of transfer of sensible heat per unit area,

and 

<3f=rate of change of heat storage per unit area

below evaporating surface.

"Thus, R— G=LE+H and, if R and G can be measured 

or estimated, the determination of E and H becomes a 

matter of correctly assigning the relative magnitudes 

of these quantities."

Other investigators have worked on the energy-budget approach to evaporation measurement (see 41, 62, 

85, 130, 162, 206, 222, 223, 227, 229, 230, 235, 283, 285, 

289, 290). E. E. Anderson (41) demonstrated that the 

evaporation computed using the energy-budget equation was in good agreement with evaporation determined from the water-budget control at Lake Hefner. 

Harbeck (130, 133) and Harbeck and Koberg (134) 

rearranged Andersen's energy-budget equation,

to determine evaporation. Their equation is simply, 

inflow— outflow= change in storage, in which

Qt = solar radiation incident to the water surface,

Qr =reflected solar radiation,

Qa =rncoming long-wave radiation from the atmosphere,

Qar= reflected long-wave radiation,

Q, =net energy advected into the body of water,

$6s=long-wave radiation emitted by the body of 

water,

Qe = energy utilized by evaporation,

Qh = energy conducted from the body of water as 

sensible heat,

Qw = energy advected by the evaporated water,

Q» = increase in energy stored in the body of water.

Some factors, such as heating due to chemical and 

biological processes, conduction of heat through the 

lake bottom, and transformation of kinetic energy into 

thermal energy are small and were neglected.

TECHNIQUES IN EVAPORATION SUPPRESSION

Where water is at a premium, as in the arid regions, 

man has resorted to various methods of conserving it. 

Freese (118), in his paper before the First International 

Conference on Eeservoir Evaporation Control, discussed a number of methods of reducing evaporation. 

Most methods consist of reducing the liquid surface 

exposed to the atmosphere, and they can be divided 

into three classes — those that reduce the surface area, 

those that mechanically cover the surface, and those 

that cover the surface with a film.

The surface area can be reduced by constructing 

reservoirs with maximum depth for a given volume 

(52, 108, 118), storing water underground (52, 108, 

118), and storing water in one large reservoir instead of 

several small ones (52, 118). Evaporation losses may 

be reduced also by proper selection of reservoir sites 

(47, 100, 108).

Mechanical covers include roofs (52, 113), floating 

rafts (52), and wind breakers (52). Fleming (113) 

describes an aluminum-covered municipal reservoir at 

Santa Ana, Calif. Although ground-water reservoirs 

generally do not have exposed surfaces, in many of 

them large quantities of water are used by phreatophytes — plants that obtain water from the zone of saturation. Therefore, large quantities of water can be 

saved by elimination of phreatophytes (se,e 47, 52, 108, 

113, 249).

Surface films, the third general classification, appear 

to be the most economical and offer the greatest potential for evaporation reduction.

Harbeck and Koberg (134) in their studies state:

Application of a film affects the terms Qbl, Qt, and <?6, but the 

net sum of the effects must be zero, or

in which the symbols with prime refer to ti«* reservoir with a 

film and the symbols without prime to the sa me reservoir without a film. If evaporation is decreased, the water-surface temperature must rise until the energy no longer being utilized for 

evaporation is returned to the atmosphere by increased back 

radiation and conduction.

Harbeck and Koberg's method (134) of evaluating 

the effectiveness of a monomolecular flm involves the 

computation of two unknowns — the evaporation and 

water-surface temperatures that woulcf have been observed if no film had been applied. Tro simultaneous 

equations are used to solve for the two unknowns, one 

based upon the energy-budget concept and the other 

upon the mass-transfer theory.

The formation of monomolecular rirface films of 

spreading oils was discovered by Agne^ Pockels (232) 

in 1891. She found that the area covered by a spreading oil, such as oleic acid, could be varied at will by 

confining the film between movable barriers placed 

across a shallow tray filled with water. Lord Rayleigh 

(241) in 1899 reviewed Miss Pockels' work and came to 

the conclusion that the oil spreads to form a film one 

molecule in thickness. During the period 1903-13, 

Henri Devaux (95) studied the effect of oil film, on water 

and the limit of its expansion. He concluded that, if 

Miss Pockels had scattered an inert ponder on the surface to render the film visible, she would have seen the 

extent to which the oil would spread. He found that 

the thickness of an oil film at the maxiirum extension is
REVIEW OF LITERATURE ON EVAPORATION SUPPRESSION 57

only a single layer of molecules and that the film will 

disappear abruptly when one tries to stretch it thinner.

Marcelin (197-205) studied the properties of benzyl 

benzoate and oleic acid and their effects on water in 

terms of the law of Gay-Lussac. He found that the 

product of the area occupied by a quantity of oleic acid 

on the surface of water and the surface pressure of the 

film is constant over the range extending from the saturated surface to that represented by a surface 28 times 

as large.

Du Nouy (105), in his 1944 article "Concerning the 

rate of evaporation of water through oriented monolayers on water," referred to his earlier (1924) work 

(104) as follows:

I should also like to mention the fact that, to my knowledge, I 

published the first paper on the influence, on the rate of evaporation of water, of a monolayer of oriented molecules. This paper 

undoubtedly escaped the attention of Dr. Langmuir, as it was 

printed in the Journal of Experimental Medicine under the misleading title .... I reported a definite slowing up of the rate 

of evaporation, but my method was crude in comparison with 

that employed by Drs. Langmuir and Schaefer.

Hedestrand (141) concluded that a monomolecular 

film of fatty acid reduced the rate of evaporation of 

water very little, if at all; however, Kideal (243) and 

Langmuir and Langmuir (176) found that fatty acids 

spread on the water surface reduce evaporation greatly. 

Kideal (244-246), Gary and Kideal (73-75), and Schofield and Rideal (258, 259) studied the effects of temperature and polar groups on the equilibrium pressure, 

investigated the mechanism and rate of spreading, and 

calculated the latent heat of fusion for some of the organic compounds by an application of the Calpeyron 

equation.

Langmuir (174) found that a small amount of oil on 

the surface of water has no appreciable effect on its 

surface tension, but when the amount of oil per unit 

area is increased beyond a certain limit, the surface film 

decreases. From this he concluded that the amount of 

oil necessary to affect the surface tension corresponds 

to a layer one molecule thick. He further reasoned 

that, since the oil spreads on the water and since the 

presence of -COOH, -CO-, or -OH groups in an organic molecule tends to render a substance soluble in 

water, these groups must have a strong affinity for 

water. This means that the molecules are standing on 

end with the functional group being dissolved in the 

water and the hydrocarbon chain extending upwards 

from the surface. He found that pure hydrocarbon 

oils (without the functional groups) do not spread on 

water but form lenses. Langmuir worked out a method 

for measuring the area occupied by a molecule on the 

water surface.

Langmuir and Langmuir (176), in their paper "The

530722—5®——3

effect of monomolecular films on the evaporation of 

ether solutions," pointed out that, using Rideal's measurements, the resistance to evaporation of water by a 

monomolecular film of oleic acid is 800 units at 25°C. 

whereas, in the absence of a film, it is 3 units. Instead 

of considering the rate of evaporation of a liquid in 

grams per square centimeter per second, they usec1 the 

reciprocal of this quantity, termed the evaporation resistance, R, in square-centimeter-seconds per g~am. 

They found cetyl alcohol had a resistance of 6f,000 

units to the evaporation of water and that the effect 

can be observed in experiments at 1 atmosphere 

pressure.

The resistance of cetyl alcohol film ranges from 

5,000 units with no wind to 1,900 units with a wind 

velocity of 1.5 meters per second. The thickners of 

the film through which diffusion must occur can be 

calculated by the equation R=hfCD, where h is the 

thickness of a film, D is the diffusion coefficient, and 

C the concentration of the diffusing substance vhen 

equilibrium is brought about by stopping diffusion, 

<7=10~8 grams per cubic centimeter for the corcentration of water in the cetyl alcohol film.

Langmuir and others (175, 178) studied the effect of 

oil lenses on water and the nature of monomolecular 

expanded films. Langmuir and Schaefer (177), in their 

paper on "Rates of evaporation of water through compressed monolayers on water," pointed out that the 

rate of escape of water molecules from the surface decreased at the ratio of about 10,000 to 1 in the presence 

of a cetyl alcohol monolayer. They decided that this 

evaporation resistance is due to an energy barrier—oil 

layers reduce evaporation by a different mechanism.

Adam (2) studied the properties and molecular structure of thin films of palmitic acid on water. His views 

confirmed those of Langmuir that the film consists of 

a single layer of molecules oriented with their COOH 

group towards the water. He concluded that the hydrocarbon molecules sink to different depths whereas 

the molecules with the COOH groups rise in the w^ter, 

so that the COOH groups are in contact with each 

other; this arrangement gives a liquid film, wherear the 

packed hydrocarbon chain normally gives a solid one.

Adam (3-29) studied the properties and molecular 

structure of thin films for several compounds. His 

book (16), especially chapter 2, is a good source of 

information on surface films.

Glazov (122,123) found that the evaporation of water 

from flat dishes in an air current is reduced by surface 

films as follows: cetyl alcohol>C8Hi7 -OH>Ci5H3 r 

COOH and C26H5i • COOH and C25H51 - COOH>saponin. 

He decided that only liquid films are effective and that 

the monomolecular layers reduce convection under the 

surface.
58 STUDIES OF EVAPORATION

Oil has been used as a retardant for evaporation for 

many years. Abbe (1) reports on the work of Onofrio, 

who used oil upon inland rivers and lakes in France to 

retard evaporation and thereby reduce the formation of 

fog. Burgess (69) studied surface-film oil to find a 

stable film with the highest spreading pressure. Gary 

and Bideal (74) studied the behavior of crystals and 

lenses of fats on the surface of water and the effect of 

temperature on the presence of a film in equilibrium.

Gilby and Heymann (121) studied the rate of evaporation of water through duplex films. In the presence 

of an oil film, wind speeds as much as 8 miles per hour 

did not increase the rate of evaporation. Guttenberg 

(127) found that the rate of spreading of oil in water 

could be expressed by R=ctk where Hs temperature in 

°C., c ranges from 9 to 19 centimeters per second, and 

k ranges from 0.63 to 0.72 centimeters per second for 

oleic, linoleic, and linolenic acids. No temperature 

effect was observed between 10° and 40°C. Hedestrand (141) concluded that the rate of evaporation of 

water does not depend on resistance to the diffusion of 

water molecules through the oil film but on the resistance of the stagnant layer of air above the liquid.

Heymann and Yoffe (145, 146) studied "the stability 

of multimolecular films of hydrocarbon oils, containing 

spreaders, on water surfaces" and found that polymerized spreaders form thick films of oil that are much 

more stable than other spreaders; some last as long as 

18 months if they are kept free from dust. Langmuir 

and Langmuir (176) showed that oils have greater resistance to evaporation than other monomolecular layers. Kohwer (251) showed that surface oil films reduce 

evaporation of water in proportion to then* thickness, 

but the relatively rapid dissipation of oil by wind, rain, 

or other agents, renders this method uneconomical for 

the conservation of large areas of water. Nelson (221) 

has a patent for the use of oil on water to prevent 

evaporation. Others have studied the effects of using 

oil to prevent evaporation (see 95, 175, 218, 233, 239, 

244, 295, and 296).

The use of multimolecular layers for suppression of 

evaporation has been studied by Bikerman (56), Langmuir (178), and others (203, 217, 233). The multimolecular films differ from the monomolecular films only in 

thickness and their properties are very similar. The 

remainder of this paper, therefore, will be concerned 

with monomolecular films.

Monomolecular layers are potentially the best evaporation suppressants (77, 79, 80, 155, 243). Intensive 

study has been made of their chemical properties (see 

43, 65, 90, 94, 181, 185, 220, 231, 260, 267, 273, 274, 278, 

300,303). Sebba and Briscoe (263) found that a freshly 

formed film of n-docosanol under a surface pressure of 47 

dynes per centimeter almost completely prevents evaporation from the water surface; but, if the film is aged 

for 20 hours at zero pressure and then compressed to 47 

dynes per centimeter, it is almost completely permeable. 

They concluded that the increased permeability results 

from association of the single molecules in the uncom 

pressed film with double molecules with a bydrophilic 

alcohol group at each end. The double molecules lie 

flat on the water surface and the film is more permeable.

Zolin (322) showed that the rate of evaporation depends on the volatility of the given component. Littlewood and Kideal (182) derived a relation between observed values of evaporation coefficients and temperature at the evaporating surface. Or this basis they 

explain the wide range in the experimental results.

The shape of the molecules that mal'e up the surface 

film (3) is important in determining ib<$ rate of evaporation. Woog (320) studied the effect of shape in stearic, palmitic, and oleic acids and his results confirmed 

those of Langmuir (177). The effect of chemical structure on the water-vapor permeability of thin films was 

evaluated by Weitzel and others (314-317). They 

found that increased length in the hydrocarbon chain of 

the fatty acids decreased permeability and that the 

steric interference of a side chain increared permeability; 

8-methylpalmitic acid permitted a 98-percent passage 

of water vapor, whereas palmitic acid permitted only a 

46-percent passage. Films formed by long-chain alcohols showed a similar decrease in permeability with increasing chain length. The steric hindrance was demonstrated by the use of esters. The permeability of 

the isomers erucic acid (cis) and brasfidic acid (trans) 

was measured. Brassidic acid greatly retarded the 

passage of water vapor, whereas erucic acid had little 

effect.

Harkins (135) found that, when polar compounds are 

added, the molecules at the interface rre oriented with 

their polar groups toward the solid and their nonpolar 

groups toward the liquid. Durham (106) concluded 

that fatty acids with main chains longer than Ci8 make 

brittle solid films on subtrates containing calcium ions 

at pH 7.5. Others (18, 105, 164, 220, 246) have studied 

the effects of molecules of different shapes on the rate of 

evaporation.

lonization hi fatty-acid monolayers on pure water has 

been studied by Betts and Pethica (54) and Sanders and 

Spink (257). The surface potentials of spread monolayers of weak acids or bases vary with their pH. This 

variation may be used to calculate the intrinsic ionization constants of the film forming molecules.

The variation in the solubility of monomolecular 

films with surface pressures was studied by Sebba and 

Briscoe (262). The surface pressure exerted by a 

film, in equilibrium in excess of the solid film forming 

substance, is not constant but varies with time. They
REVIEW OP LITERATURE ON EVAPORATION SUPPRESSION 59

^tudied the following film forming materials: cetyl 

"»lcohol, octadecyl alcohol, cholesterol, proteins, and 

dearie, palmitic, oleic, elaidic, brassidic, and erucic 

•>cids. Dervichian (92) determined the film pressures, 

ilm potential compression at various temperatures, 

i.nd dipole moments of several monomolecular layers, 

"larkins and Boyd (136) studied the effect of pressures 

<md temperatures and the detection of phase transitions in monolayers for pentadecylic, palmitic, marTaric, stearic, nonadecanoic, and arachidic acids at 

surface pressures of 0-28 dynes per centimeter and 

"iscosities of 3X10~4 to 1 surface poise. They (137) 

ilso analyzed the interpretations of Dervichian.

Nutting and Harkins (224) measured the pressureirea relation of monolayers of fatty acids with 14 to 20 

carbon atoms at 25°C. and straight-chain alcohols 

Tith 14 to 18 carbon atoms at 20°C. The pressure of 

the transition point, liquid to plastic solid, increases 

from 6.2 dynes per centimeter for 14 carbon chains to 

12.2 dynes per centimeter for 18 carbon chains in the 

alcohol at 20°C.; the corresponding change for the 

acids at 25 °C. is from 21 dynes per centimeter for 15 

carbon chains to 20 dynes per centimeter for 19 carbon 

chains.

Rosano and LaMer (253) investigated the effect of 

employing monolayers of Ci7, C18, Ci9, and C20 members of the saturated fatty-acid series on evaporation. 

They found that evaporation was independent of the 

surface pressure of these monolayers in the range 10-24 

dynes per centimeter if the film was spread initially 

under pressure to prevent the entrance of impurities. 

They measured the surface area, the resistance to 

evaporation, and the surface viscosity for each substance as a function of the surface pressure. Shishakov 

(268), in his paper "Electronography as a method for 

the physical chemistry of surface film," gives an 

annotated bibliography. Others (34, 35, 91, 110, 143, 

160, 167, 200, 201, 202, 205, 211, 242, 243, 256, 286, 302, 

and 314) have studied the effects of surface pressure 

and surface tension on evaporation.

Viscosity of monomolecular films was studied by 

Joly (156-159) and others (67, 93, 94, 111, 138, 254). 

Joly investigated films of palmitic acid, oleic acid, and 

tricaproin and drew conclusions about the arrangement 

of their carbon chains that explain the increase in 

viscosity with molecular area. The viscosity measurements can give precise information on the equilibrium form of the molecules, the forces of molecular 

interaction, and the energetics of surface phenomena. 

He listed 120 references.

The effect of monolayers on the rate of evaporation 

has been investigated by many men (119, 142,143,144, 

176, 214, 243, 264, and 265). Archer and LaMer (45, 

46) studied the resistance to evaporation of monolayers

of 4 fatty acids of 17, 18, 19, and 20 carbon atoms. 

Their measurements indicated that the monolayers 

decreased the rate of evaporation of water by a factor 

of about 104. Baranaev (48) found that the ratio of 

evaporation of pure and film-covered water could be 

expressed by the equation, V—e—aFofT, where T is 

temperature and values of a and FQ were given in dynes 

per centimeter. Values of a and F$ were obtained as 

follows: cetyl alcohol, 55.0, 40; hexadecyl acetate, 53.4, 

34; palmitonitrile, 53.0, 13.5; palmitic acid, 52.0, 10.0; 

stearic acid, 54.2, 6.0; lauric acid, 26.9, 20.0; and c^eic 

acid, 17.1, 29.0. Baranaev (48) derived a formula on 

the assumption that evaporation takes place through 

"holes" in the monolayers.

Bartlett and Poulter (51) studied the influence of 

surface tension on the rate of evaporation of water 

through surface films. Kheinman's (163) studies indicate that cetyl alcohol decreases the rate of evaporation. 

A 0.5N solution of sodium oleate has no effect; but, 

when excess solid sodium oleate is present, evaporation 

is decreased. Paraffin has no effect, but crude petroleum has. Glazov (122, 123) determined the rate of 

evaporation for several surface-active substances. He 

found that a monomolecular layer of cetyl alcohol causes 

the largest decrease in evaporation when compared 

with the effect of aliphatic acids, aromatic amines, and 

other surface-active substances.

The early investigators considered that all sur'ace 

films were either oils or monomolecular layers; however, 

a better classification would be oils, multimolecMlar 

layers, and monomolecular layers.

Early investigations (48, 50, 122,176) of monomcJecular films have shown that cetyl alcohol has the greatest resistance to evaporation. Docking and others 

(97) found in their experiments that cetyl and octadecyl 

alcohol reduced evaporation, and these authors vere 

the first to apply the film on ponds and reservoirs for 

the control of evaporation. They studied the effects 

of some multimolecular films which were not successful 

during field experiments.

Mansfield (192) in 1953 experimented with flakes of 

cetyl alcohol on reservoirs but found them to be unwritable. The East African Industrial Research Organization (107) describes a method for pelletizing cetyl 

alcohol. Mansfield (193, 195) used the pellets successfully in his laboratory and field tests during the 1954-55 

season. He placed alcohol pellets in a small raft 

covered with wire gauze. The initial dosage was estimated to be 3 to 5 pounds per acre. Heath (140) in 

his article describes the standard method of pelletizing 

cetyl alcohol.

Laycock (179) used small wood rafts to dispense 

pellets of cetyl alcohol at the^rate of 1 pound per acre 

to form a thin film that reduced evaporation from 50
60 STUDIES OF EVAPORATION

to 70 percent. He found that the method is harmless 

to fish and other annual life but that it inhibits development of mosquito larvae. Downing and Melbourne 

(99) studied the effect of hexadecyl alcohol on natural 

waters and found that it reduced the rate of solution 

of oxygen. They suggested that

in the development of the use of cetyl alcohol, due regard should 

be given to this potential effect, particularly where reservoirs 

contain high concentrations of organic matter, the decay of which 

could create a high oxygen demand.

Boon and Downing (63) found that the efficiency of 

hexadecyl alcohol in reducing evaporation depends on 

intensity of solar radiation, wind velocity, relative humidity, the rate at which films are replaced, and biological action.

Grundy (126) studied the use of kerosene for dispersing cetyl alcohol. He found

success in the use of the solution depends on wind, even a light 

breeze, to carry drops of the liquid over the water surface. 

The principle by which the film is spread is as follows: when 

some of the solution is poured on a water surface, it breaks up 

into drops. The first drops disperse rapidly to spread a film as 

much as 100 feet from the point of dosing. Additional drops 

of solution will not disperse in the presence of a film but are carried down wind to areas of water surface with no film, where they 

in turn disperse. This process is repeated across the reservoir if 

enough solution is used. The solution damps small waves, so 

the progress of the spreading film can be observed visually across 

the reservoir.

He found that evaporation was reduced 20 percent by 

a dose of 1 liter of solution per day on a 1-acre reservoir. A second experiment on a 5-acre reservoir dosed 

with 3 liters per day and wind velocities as much as 15 

miles per hour showed a reduction in evaporation of 

slightly more than 30 percent.

McArthur and Durham (189) believe that the use of 

a mixture of cetyl and stearyl alcohol is more effective 

than cetyl alcohol alone in reduction of evaporation of 

water from reservoirs in hot climates. They found 

that the addition of 5-8 percent of oleyl alcohol improves the spreading and recovery rates, but spreading 

agents, such as octanol or Pluronic F68, are unnecessary 

and greatly reduce the effect of the film.

Several organizations in the United States have been 

studying evaporation suppression. The following have 

reported on their progress: Southwest Research Institute (101, 102, 103, 169, 249), the U.S. Bureau of Reclamation (77, 291, 292, 293, 307, 308, and 309), the U.S. 

Geological Survey (133,134), and others (248, 276, 277).

The Southwest Research Institute began studies in 

1955. Dressier (100, 103) used an insulated metal 

trough filled with water whose temperature was kept

at 30°C. Eighteen battery jars containing distilled 

water were placed in the trough. He left one or more 

jars untreated as a control. Dried air was blown over 

the jars at a rate of about 0.1 mile p^r hour. Water 

levels were maintained and replenishment was measured 

to determine evaporation loss. He studied about 150 

potential evaporation retardants and found that hexadecanol and octadecanol gave good results. The U.S. 

Geological Survey (132) measured evaporation from a 

3-acre ranch pond near Southwest Research Institute, 

both with and without a film.

The U.S. Bureau of Reclamation and U.S. Public 

Health Service studied evaporation suppression on Kids 

Lake in 1956 (293) and found that hexadecanol did not 

affect the water quality, including taste, odor, color, and 

toxicity. From this they concluded that it was feasible 

to treat Lake Heftier. Berger (53) studied the effects 

of hexadecanol and found that it was not toxic to fish and 

did not create problems for water treatment processes. 

Timblin (291) worked out a series of indicator oils which 

shows the presence and degree of compression of a monomolecular layer. A modified method used talc-powder 

(205) as an indicator for detection on small areas. The 

Bureau of Reclamation reported reduction in evaporation losses of as much as 65 percent ri field studies on 

Rattlesnake Reservoir (77, 292) in Colorado.

The Bureau of Reclamation (307-309) studied the 

effect of surface tension on the flotation of small beads 

hexadecanol, screening tests on monolryers and duplex 

films, and other properties of mononolecular layers. 

Ludzack and Ettinger (186) studied the biological oxidation of hexadecanol under laboratory conditions and 

reported measurable consumption of the material with 

all substrates tested. LaMer and Robbins (170, 173) 

have studied the effects of solvents in the spreading of 

monolayers. The Geological Survey is searching for 

a suitable solvent.

A significant part of our water suppH is lost through 

evaporation; Meyers estimates the annual evaporation 

loss in 11 western States is 11.5 million acre-feet (210) 

and the total water use of the same States amounts to 

111 million acre-feet. Dressier (78) found that monomolecular films are especially suitable for the large western reservoirs. He estimated that

the cost, including chemicals, amortization o* equipment, labor, 

and power, totals $4.50 per acre-foot of water saved, or 1.4 cents 

per 1,000 gallons, operating 180 days per ye*r. This compares 

with values of about $6.00 per acre-foot for irrigation water and 

$10.00 to $40.00 per acre-foot for municipal ^rater.

Dressier thinks that 40 percent of the water normally 

lost by evaporation could be saved.
REVIEW OF LITERATURE ON EVAPORATION SUPPRESSION 61

BIBLIOGRAPHY

[References marked with an asterisk (*) contain bibliographies on 

evaporation suppression. Abstracts of most references are 

available in the Chemical Abstracts of the American Chemical 

Society, the British Abstracts, and the Water Pollution Abstracts of the Department of Scientific and Industrial Research, 

London. Transliterations of names of authors and publications have followed the usage of these abstracts for ease of 

reader reference]

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62 STUDIES OF EVAPORATION

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REVIEW OF LITERATURE ON EVAPORATION SUPPRESSION 63

77. Chemical and Engineering News, 1957, Chemical shields to 

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78. Chemical and Engineering News, 1958, Film protects climate's prey: v. 36, no. 26, p. 44-45.

79. Chemical Week, 1955, Australians have developed a trick to 

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80. Chemical Week, 1955, Control on water: v. 77, no. 9, p. 18.

81. Chemical Week, 1957, Process plants plan for future water 

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64 STUDIES OF EVAPORATION

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REVIEW OF LITERATURE ON EVAPORATION SUPPRESSION 65

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66 STUDIES OF EVAPORATION"

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REVIEW OF LITERATURE ON EVAPORATION SUPPRESSION 67

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68 STUDIES OF EVAPORATION

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EEVIEW OF LITERATURE ON EVAPORATION SUPPRESSION 69

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o