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1490 II / FLOTATION / Dissolved Air

E De-sanding hydrocyclones are now being installed First Hydrocyclone Conference, Cambridge (UK) (1980)
upstream from the choke in some Relds. There Priestley G and Stephens HS (eds). CranReld: BHRA.
could be an energy saving if de-sanding and de- Second Hydrocyclone Conference, Bath (UK) (1984) Watts
oiling could be performed in a single unit, but GA and Pickford R (eds). CranReld: BHRA.
simultaneous optimization of both functions is un- Third Hydrocyclone Conference, Oxford (UK) (1987)
Wood P (ed.). CranReld: Elsevier-BHRA.
likely. A successful laboratory research project has
Fourth Hydrocyclone Conference, Southampton (UK)
been reported in France, but initial Reld trials in (1992) Svarovsky L and Thew MT (eds). Dordrecht:
West Africa were disappointing. Kluwer.
E Heavy oils, i.e. those with a higher density and Hydrocyclones 96 Conference, Cambridge (UK) (1996)
viscosity, appear unpromising for cyclonic separ- Claxton D, Svarovsky L and Thew MT (eds). London:
ation processes. Nevertheless success has been re- MEP.
ported for commercial de-oiling units used in the Vortex Separation: Fifth International Conference on Cyc-
concentrator mode in trials in western Canada. lone Technologies, Warwick (UK) (2000) Svarov-
E Feasibility studies and preliminary Reld trials are in sky L and Thew MT. Organised and published by
progress on integrated de-watering plus de-oiling BHR Group, CranReld.
cyclonic separation and/or de-sanding plus de-oil- Meldrum N (1987) Hydrocyclones: a solution to produced
water treatment. Proceedings of the 19th Annual
ing. The attraction is an ultra-compact plant suited
Offshore Technology Conference, Houston, Texas,
particularly to Soating installations. Though de- USA.
watering units have not yet met with widespread Paige R and Ferguson M (1993) Water injection:
success, the impending arrival of compact, robust practical experience and future potential (A BP
electrocoalescers to raise water droplet size prior to Study). Conference on Offshore Water and Envir-
separator entry, could transform the situation. onmental Management. Business Seminars Interna-
E With success in dealing with petroleum it is surpris- tional, London.
ing that applications to edible oils, which are about Smyth IC and Fay B (1998) Further developments of the
10 times more valuable, have yet to materialize. HydrosepTM System for downhole oil/water separation.
Laboratory trials have been very satisfactory. Not Conference on Downhole Production and Subsea Pro-
only is lost oil a revenue drain but it generates cessing, Aberdeen. Organised by BHR Group, London:
MEP.
a potential environmental hazard.
Svarovsky L (1984) Hydrocyclones. London: Holt,
Rinehart and Winston.
Further Reading Young GAB, Wakley WD et al. (1994) Oil-water separ-
ation using hydrocyclones: an experimental search for
Note: The Rve conferences on hydrocyclones all contain optimum dimensions. Journal of Petroleum Science 11:
several papers on oil}water hydrocyclones 37}50.

Dissolved Air
D. Shekhawat and P. Srivastava, suspended material present in the aqueous stream,
Michigan State University, East Lansing, MI, USA causing them to Soat to the surface, where they are
Copyright ^ 2000 Academic Press collected as Soc.
DAF can be carried out by vacuum or pressurized
methods. In the vacuum Sotation method the water
Introduction to be treated is saturated with air at atmospheric
Dissolved air Sotation (DAF) is a solid}liquid separ- pressure. The bubbles are produced by applying a
ation process for the removal of Rne suspended vacuum to the Sotation tank, releasing the air as Rne
material from an aqueous suspension. The basic prin- bubbles. The vacuum Sotation process has several
ciple underlying DAF is Henrys law, which gives disadvantages. These are (a) the amount of air avail-
the solubility of air in water. According to Henrys able for Sotation is limited by the vacuum achievable,
law, the solubility of air in water is directly propor- (b) it is a batch process, and (c) it requires special
tional to its partial pressure. A supersaturated solu- equipment to produce and to maintain high vacuum.
tion of water is produced using high pressure in These disadvantages limit the application of vacuum
a saturator. The bubbles are generated by the pressure Sotation and it is only used in wastewater sludge
release of this water stream. These bubbles attach to thickening.
II / FLOTATION / Dissolved Air 1491

The pressure Sotation process is the most widely Disadvantage


used DAF technique. High pressure water is saturated
1. DAF processes are more costly to operate and
with air. This pressurized water forms small bubbles
maintain than sedimentation processes.
when injected into water at atmospheric pressure.
Three types of pressurization processes can be used
in DAF: full Sow, partial Sow and recycle Sow Process Description
pressurization. The entire inlet stream is pressurized A schematic diagram of a DAF process for wastewater
in full Sow pressure DAF. It is commonly used treatment is shown in Figure 1. Its essential elements
when the wastewater contains large amounts of sus- are a Socculation tank, a Sotation tank, an air com-
pended solids and the pressurization process does pressor, an air saturator, a recycling pump and a hy-
not affect the treatment efRciency of the sys- drosweep system. The wastewater is pumped to the
tem. Partial Sow pressurization is used where Socculation tank after being treated with coagu-
the wastewater contains moderate to low concentra- lant/Socculent agents such as aluminium sulfate.
tions of suspended solids. In the recycle Sow pressur- A portion of the clariRed efSuent is recycled for
ization system, 10}25% of the clariRed efSuent pressurization. Compressed air is introduced into the
is recycled through a pressure vessel to the discharge stream of the recycle pump, and the water is
Sotation tank. The Socculation process in not saturated with air at high pressure. The pressurized
disturbed in the recycle Sow system because of in- water stream is introduced to the Sotation tank
tense mixing and pressurization as clear water is through nozzles, where Rne bubbles (20}100 m) in
pumped. A recycle Sow system is cost-efRcient diameter are formed. The bubbles attach themselves to
because it pressurizes only part of the water, thus suspended solid particles, causing the agglomerates to
requiring less compressor power. Recycle Sow pres- Soat to the surface of the tank. The Soat can be mechan-
sure Sotation is the best-suited system for most DAF ically skimmed from the surface, and the clariRed water
applications. is taken from the bottom of the Sotation tank.
DAF is an effective alternative to sedimenta-
tion. The advantages and disadvantage of DAF rela-
tive to sedimentation are as follows: Principles of Dissolved Air Flotation
DAF facilities are composed of the following four
Advantages principal steps:

1. ClariRcation rates are higher in DAF, resulting in 1. coagulation and Socculation prior to Sotation
smaller Socculation tank volumes. 2. bubble generation
2. More concentrated sludge solids are produced in 3. bubble}Soc collision and attachment in the mixing
DAF than from sedimentation. zone
3. DAF uses lower amounts of coagulants and Soccu- 4. rising of the bubble}Soc aggregates in a Sotation
lent aids. tank
4. Oxygenation effects in DAF reduce odour
Coagulation and Flocculation Prior to Flotation
problems.
5. DAF provides better removal of low density par- Coagulation and Socculation are often considered as
ticles and algae, which can plug Rlters. a pretreatment step in DAF processes. Favourable

Figure 1 Schematic diagram of the dissolved air flotation process for water treatment.
1492 II / FLOTATION / Dissolved Air

conditions for bubble attachment to particles requires Classically, the contact angle between the adsorbed
coagulation conditions that reduce particle charge bubble and particle has been used to characterize the
and produce hydrophobic particles. Coagulant dos- extent of bubble}Soc adhesion. Here the contact
ages and pH conditions that satisfy these criteria angle must be Rnite and large enough that the energy
depend on the coagulant type and raw water charac- of adhesion of water to the solid particle is less than
teristics, including particle concentration, hardness, the energy of cohesion of water. A larger contact
and concentration and type of natural organic matter angle indicates both hydrophobicity and good ad-
(NOM). Unlike in sedimentation, large Soc particles hesion. The magnitude of the contact angle, however,
are not needed in DAF. Flocculation tanks are de- depends on the size of the bubbles and particles.
signed to produce strong Socs with particle size distri- A different view of particle}bubble attachment
butions of 10}30 m and short Socculation times, in of colloidal particles by small bubbles is that a Rnite
the range of 10}15 min. contact angle need not form. In this heterocoagula-
tion model, the stability of charged particles and
Bubble Generation bubbles is described. Attachment requires reduction
Small air bubbles, 100 m or less, are formed by in electrical charge interactions and attraction by
injection of supersaturated pressurized recycle water London}van der Waals forces as particles are trans-
into a Sotation tank using specially designed nozzles. ported to bubble surfaces.
The process of bubble formation involves two steps: Both the contact angle and the heterocoagulation
nucleation and growth. During the Rrst step the large models predict experimentally observed trends that
pressure difference across the nozzle produces two conditions are necessary for favourable Sotation:
bubble nuclei spontaneously. Air bubbles grow at charge neutralization of the particles and production
a Rxed number of nucleation centres due to air trans- of hydrophobic particles. Bubble attachment to par-
ferred from the water. As the excess air is transferred ticles requires hydrophobic particle surfaces or hy-
from the dissolved to the gas phase, the bubbles grow drophobic regions on the particles. For many par-
in size. Additional bubble growth may occur as the ticles, hydrophobicity can be increased by reducing
bubbles rise due to a decrease in hydrostatic pressure the negative charge. Other particles, such as freshly
or coalescence. precipitated or amorphous Al(OH)3, have polar
Measurements of bubble sizes for DAF systems surface groups that make them hydrophilic. This
indicate that bubbles maintain a steady-state size hydrophilic effect may be reduced by charge
range of 10}100 m. A reasonable estimate of aver- neutralization, but aluminium hydroxide particles
age bubble diameter is 40 m. The steady-state size have a polymolecular coating of water which hinders
depends on the saturator pressure and the injection bubble adhesion.
Sow rate. The injection Sow must provide a rapid
pressure drop and be sufRcient to prevent back- Rising of the Bubble+Floc Aggregates in
Sow and bubble growth on pipe surfaces in the vicin- a Flotation Tank
ity of the injection system. To ensure small bubbles, Following bubble attachment and reduction in
pressure differences (saturator gauge pressures) of particle density, particle}bubble agglomerates rise
400}600 kPa are recommended. to the surface of the Sotation tank in the separation
or clariRcation zone. The rise velocity of the
Bubble Floc Collision and Attachment in particle}bubble agglomerate may be calculated using
the Mixing Zone
Stokes law.
There are three possible mechanisms for forming ag-
gregates of bubbles and particles:
DAF Modelling
1. entrapment of preformed bubbles in large Soc The design and operation of DAF facilities has largely
structures (Soc size much larger than bubble size been based on experience and results from pilot-plant
scale) studies. In recent years, a conceptual model of DAF
2. growth of bubbles whose nuclei formed on par- has been developed, based on a single collector colli-
ticles or within Socs sion theory in laminar Sow conditions (SCC model).
3. particle collision with adhesion to preformed A kinetic model has also been presented, based on the
bubbles population balance model of bubbles and Socs in
a turbulent Sow condition (PBT model).
For DAF processes, the third mechanism is the most For modelling purposes, DAF processes can be
important. divided into two zones: reaction zone (regions where
II / FLOTATION / Dissolved Air 1493

the saturated recycle Sow is introduced) and separ- agglomerate rising velocity), is deRned by the
ation zone. Soc}bubble agglomerate size (dflb) and density (flb)
(eqn [2]). These are dependent on the Soc size}density
Reaction Zone Modelling ratio and concentration, and the size and number of
For the reaction zone efRciency (dNfl/dt), deRned bubbles comprising the Soc}bubble agglomerate:
as the reduction of number of primary particle Socs
with time, Soc and bubble size (dfl and db) and con- vflb"gdflb(pw!pflb)/18  [2]
centration are deRned as relevant process parameters:
Eqn [3] represents a necessary prerequisite for ef-
Rcient DAF, vos being the DAF overSow rate and
dNfl/dt"!(3/2)(pb T)(bvb Nfl)/db [1]
m being the fraction of DAF tank dead space:
where pb"particle bubble attachment efRciency; vflb'vos /(1!m) [3]
T"total single collector efRciency; db"bubble
diameter; vb"bubble rise velocity; Nfl"Soc number
concentration; b"bubble volume concentration. Applications of Dissolved Air Flotation
Particle (Soc)}bubble interception is considered to DAF is best applied to remove materials that normal-
be the most relevant kinetic mechanism for DAF ly settle slowly, persist in remaining in suspension or
efRciency, depending on the Soc and bubble size have a tendency to Soat. Prior to the 1960s it was
(dn and db) and incorporated in T. This term also mainly utilized in the area of mining and metallurgi-
considers Soc}bubble collision mechanisms related to cal industries. Now, DAF Rnds numerous applica-
Brownian diffusion, settling and drag. tions, e.g. mineral processing, water puriRcation,
A summary of these parameters, their dependence wastewater treatment, waste sludge thickening,
on the system variables and desirable operational wastewater reclamation, recycled paper de-inking,
conditions is given in Table 1. and many more. It is widely used for drinking water
puriRcation in many Scandinavian countries, South
Separation Zone Modelling
Africa, the Netherlands, the UK and others. In drink-
Assuming laminar Sow conditions, the efRciency ing water clariRcation, DAF has been applied in
of the separation zone, vflb (deRned as Soc}bubble combination with Socculation for the removal of

Table 1 Summary of conceptual reaction zone model parameters

Parameter Dependence Comments

Pretreatment parameters
pb (particle}bubble attachment efficiency) 1. Particle}bubble charge interactions 1. Favourable flotation; requires
reduction in particle charge and
hydrophobic particles
2. Hydrophilic nature of particles 2. Increase pb to 1: optimum coagulation
and charge neutralization
Np (particle number concentration) 1. Raw water quality 1. Concentration and size of particles;
concentration of NOM
2. Coagulant type and conditions 2. Coagulants may add particles
3. Flocculation time 3. Flocculation may reduce Np and
increase dp
Reaction zone}flotation tank
T (total single collector efficiency) 1. Particle}bubble collisions from diffusion 1. Increase T : produce floc size of
and interception tens of m
2. Minimum T for dp of &1 m 2. Short flocculation times
d b (bubble diameter) Controlled by pressure difference across 1. Desire microbubbles: range
nozzle and injection flow 10}100 m, median 40 m;
smaller bubbles: better performance
2. T varies as d b\2; rate of collection of
particles varies as d \b
1

b (bubble volume concentration 1. Saturator pressure 1. Increasing b increases Np: more


bubbles for collection of particles
2. Recycle ratio 2. Increase b: more bubble volume for
reducing floc density

Reproduced with permission from Edzwald (1995).


1494 II / FLOTATION / Electrochemistry: Contaminant Ions and Sul\de Mineral Interactions

algae and humic substances. The Rrst water treatment design and operation of DAF methods are currently
plant based on the DAF process was established in tested on empirical data and data from costly and
South Africa in 1969. Since then it has received time-consuming pilot-plant models. More informa-
worldwide attention for research and development on tion is needed on the performance, designs and costs
all aspects of DAF. of the DAF process.
The Rrst DAF plant in the USA was set up at the
Millwood water treatment plant in Westchester See also: I/Flotation.
county (35 miles north of New York city) in August
1993. Now, several other plants based on DAF are Further Reading
operating or are under study in the USA. It is postu- Derjaguin BV, Dukhin SS and Rulyov NN (1984) Kinetic
lated that DAF is an emerging technology in the USA theory of Sotation of small particles. In: Matijevic E and
that will become more important because of existing Good RJ (eds) Surface and Colloid Science, vol. 13, New
and proposed regulations that require Rltration of York: Plenum Press, pp. 71}113.
surface waters and increased removal of protozoa Edzwald JK (1995) Principles and application of
cysts such as Cryptosporidium and Giardia. Large dissolved air Sotation. Water Science and Technology
scale pilot-plant trials of water treatment have been 31: 1}23.
Edzwald JK, Malley JP and Yu C (1991) A conceptual
carried out in the UK for removal of Cryptosporidium
model for dissolved air Sotation in water treatment.
using DAF. Well-operated chemical coagulation- Water Supply 9: 141}150.
based treatment using DAF should be capable of Fukushi K, Tambo N and Matsui Y (1995) A kinetic
achieving 99% removal of Cryptosporidium model for dissolved air Sotation in water and waste-
oocysts. water treatment. Water Science and Technology 31:
DAF is also used in the forest industry, food- 37}47.
stuff industry, meat-processing industry, seafood Hall H, Pressdee J, Gregory R and Murray K (1995)
industry, potato processing, pulp and paper industry, Cryptosporidium removal during water treatment using
petroleum industry, poultry industry, producing re- dissolved air Sotation. Water Science and Technology
Rned sugar from raw juices, separation of grease, oil, 31: 125}136.
Rbres and other low density solids, chemical process- Ives KJ and Bernhardt HJ (eds) (1995) Flotation processes
in water and sludge treatment. Water Science and Tech-
ing plants, storm water cleaning, and other similar
nology 31.
industries. Kitchener JA and Gochin RJ (1981) The mechanism of
dissolved air Sotation for potable water: basic analysis
Future Trends and proposal. Water Research 15: 585}590.
Takahashi T, Miyahara T and Mochizuki H (1979) Funda-
There is great potential for DAF. Its use has been mental study of bubble formation in dissolved air pres-
limited due to lack of knowledge of the process by sure Sotation. Journal of Chemical Engineering, Japan
users, designers and other regulatory agencies. The 12: 275}280.

Electrochemistry: Contaminant Ions and Sul\de Mineral


Interactions
J. T. Smit and J. Gnoinski, from their typical hydrophilic nature to hydrophobic,
Anglo American Research Laboratories (Pty) Ltd., to which the gas bubbles may attach to effect the
Johannesburg, South Africa levitation. This conversion is usually achieved by the
R. F. Sandenbergh, University of Pretoria, selective attachment of collectors to the surface of
Pretoria, South Africa the mineral or by natural processes; an example
Copyright ^ 2000 Academic Press of the latter is the formation of elemental sulfur or
a metal-deRcient sulRde layer on sulRdes.
Typical collector agents are organic substances con-
Introduction sisting of an ionic, i.e. hydrophilic, end that attaches to
Mineral separation by Sotation is based on the selec- the mineral and a nonionic hydrocarbon end that
tive levitation and separation of mineral particles by creates the hydrophobicity of the mineral surface.
gas bubbles. This is carried out by the selective con- A widely used collector in selective sulRde Sotation is
version of the surfaces of the minerals to be Soated the xanthate ion (O-alkyldithiocarbonate, ROCS2).
Henry'slaw
FromWikipedia,thefreeencyclopedia

Inchemistry,Henry'slawisoneofthegaslawsformulatedbytheEnglishchemistWilliamHenry,who
studiedthetopicintheearly19thcentury.Inhispublicationaboutthequantityofgasesabsorbedbywater,[1]
hedescribedtheresultsofhisexperiments:

..."watertakesup,ofgascondensedbyone,two,ormoreadditionalatmospheres,aquantitywhich,
ordinarilycompressed,wouldbeequaltotwice,thrice,&c.thevolumeabsorbedunderthecommon
pressureoftheatmosphere."

Inotherwords,theamountofdissolvedgasisproportionaltoitspartialpressureinthegasphase.The
proportionalityfactoriscalledtheHenry'slawconstant.

AnexamplewhereHenry'slawisatplayisinthedepthdependentdissolutionofoxygenandnitrogeninthe
bloodofunderwaterdiversthatchangesduringdecompression,leadingtodecompressionsickness.An
everydayexampleisgivenbyone'sexperiencewithcarbonatedsoftdrinks,whichcontaindissolvedcarbon
dioxide.Beforeopening,thegasabovethedrinkinitscontainerisalmostpurecarbondioxide,atapressure
higherthanatmosphericpressure.Afterthebottleisopened,thisgasescapes,movingthepartialpressureof
carbondioxideabovetheliquidtobemuchlower,resultingindegassingasthedissolvedcarbondioxidecomes
outofsolution.

Contents
1 FundamentaltypesandvariantsofHenry'slawconstants
1.1 Henry'slawsolubilityconstants
1.2 Henry'slawvolatilityconstants
2 ValuesofHenry'slawconstants
3 Temperaturedependence
4 EffectiveHenry'slawconstants
5 Dependenceonionicstrength(Sechenovequation)
6 Nonidealsolutions
6.1 Solventmixtures
7 Miscellaneous
7.1 Ingeochemistry
7.2 ComparisontoRaoult'slaw
8 Seealso
9 References
10 Externallinks

FundamentaltypesandvariantsofHenry'slawconstants
TherearemanywaystodefinetheproportionalityconstantofHenry'slaw,whichcanbesubdividedintotwo
fundamentaltypes:Onepossibilityistoputtheaqueousphaseintothenumeratorandthegasphaseintothe
denominator("aq/gas").[2]ThisresultsintheHenry'slawsolubilityconstant .Itsvalueincreaseswith
increasedsolubility.Alternatively,numeratoranddenominatorcanbeswitched("gas/aq"),whichresultsinthe
Henry'slawvolatilityconstant .Thevalueof decreaseswithincreasedsolubility.Thereareseveral
variantsofbothfundamentaltypes.Thisresultsfromthemultiplicityofquantitiesthatcanbechosento
describethecompositionofthetwophases.Typicalchoicesfortheaqueousphasearemolarconcentration( ),
molality( ),andmolarmixingratio( ).Forthegasphase,molarconcentration( )andpartialpressure( )are
oftenused.Itisnotpossibletousethegasphasemixingratio( )becauseatagivengasphasemixingratio,the
aqueousphaseconcentration dependsonthetotalpressureandthustheratio isnotaconstant.[3]To
specifytheexactvariantoftheHenry'slawconstant,twosuperscriptsareused.Theyrefertothenumeratorand
thedenominatorofthedefinition.Forexample, referstotheHenrysolubilitydefinedas .

Henry'slawsolubilityconstants

Henrysolubilitydefinedviaconcentration( )

AtmosphericchemistsoftendefinetheHenrysolubilityas

.[2]

Here istheconcentrationofaspeciesintheaqueousphase,and isthepartialpressureofthatspeciesinthe


gasphaseunderequilibriumconditions.

TheSIunitfor ismol/(m3Pa)however,oftentheunitM/atmisused,since isusuallyexpressedinM


(1M=1mol/dm3)and inatm(1atm=101325Pa).

ThedimensionlessHenrysolubility

TheHenrysolubilitycanalsobeexpressedasthedimensionlessratiobetweentheaqueousphaseconcentration
ofaspeciesanditsgasphaseconcentration :

.[2]

Foranidealgas,theconversionis:

,[2]

where isthegasconstantand isthetemperature.

Sometimes,thisdimensionlessconstantiscalledthe"waterairpartitioningcoefficient" .Itisclosely
relatedtothevarious,slightlydifferentdefinitionsofthe"Ostwaldcoefficient" ,asdiscussedbyBattino
(1984).[4]

Henrysolubilitydefinedviaaqueousphasemixingratio( )

AnotherHenry'slawsolubilityconstantis

.[2]

Here isthemolarmixingratiointheaqueousphase.Foradiluteaqueoussolutiontheconversionbetween
and is:

,[2]

where isthedensityofwaterand isthemolarmassofwater.Thus

.[2]

TheSIunitfor isPa1,althoughatm1isstillfrequentlyused.[2]
Henrysolubilitydefinedviamolality( )

Itcanbeadvantageoustodescribetheaqueousphaseintermsofmolalityinsteadofconcentration.The
molalityofasolutiondoesnotchangewith ,sinceitreferstothemassofthesolvent.Incontrast,the
concentration doeschangewith ,sincethedensityofasolutionandthusitsvolumearetemperature
dependent.Definingtheaqueousphasecompositionviamolalityhastheadvantagethatanytemperature
dependenceoftheHenry'slawconstantisatruesolubilityphenomenonandnotintroducedindirectlyviaa
densitychangeofthesolution.Usingmolality,theHenrysolubilitycanbedefinedas

Here isusedasthesymbolformolality(insteadof )toavoidconfusionwiththesymbol formass.TheSI


unitfor ismol/(kgPa).Thereisnosimplewaytocalculate from ,sincetheconversionbetween
concentration andmolality involvesallsolutesofasolution.Forasolutionwithatotalof soluteswith
indices ,theconversionis:

where isthedensityofthesolution,and arethemolarmasses.Here isidenticaltooneofthe inthe


denominator.Ifthereisonlyonesolute,theequationsimplifiesto

Henry'slawisonlyvalidfordilutesolutionswhere and .Inthiscasetheconversion


reducesfurtherto

andthus

TheBunsencoefficient

AccordingtoSazonovandShaw,thedimensionlessBunsencoefficient isdefinedas"thevolumeof
saturatinggas,V1,reducedtoT=273.15K,p=1bar,whichisabsorbedbyunitvolumeV2*ofpuresolvent
atthetemperatureofmeasurementandpartialpressureof1bar."[5]Ifthegasisideal,thepressurecancelsout,
andtheconversionto issimply

with =273.15K.Note,thataccordingtothisdefinition,theconversionfactorisnottemperature
dependent.IndependentofthetemperaturethattheBunsencoefficientrefersto,273.15Kisalwaysusedforthe
conversion.TheBunsencoefficient,whichisnamedafterRobertBunsen,hasbeenusedmainlyintheolder
literature.

TheKuenencoefficient
AccordingtoSazonovandShaw,theKuenencoefficient isdefinedas"thevolumeofsaturatinggasV(g),
reducedtoT=273.15K,p=bar,whichisdissolvedbyunitmassofpuresolventatthetemperatureof
measurementandpartialpressure1bar."[5]Ifthegasisideal,therelationto is

where isthedensityofthesolvent,and =273.15K.TheSIunitfor ism3/kg.[5]TheKuenen


coefficient,whichisnamedafterJohannesKuenen,hasbeenusedmainlyintheolderliterature,andIUPAC
considersittobeobsolete.[6]

Henry'slawvolatilityconstants

TheHenryvolatilitydefinedviaconcentration( )

AcommonwaytodefineaHenryvolatilityisdividingthepartialpressurebytheaqueousphaseconcentration:

TheSIunitfor isPam3/mol.

TheHenryvolatilitydefinedviaaqueousphasemixingratio( )

AnotherHenryvolatilityis

TheSIunitfor isPa.However,atmisstillfrequentlyused.

ThedimensionlessHenryvolatility

TheHenryvolatilitycanalsobeexpressedasthedimensionlessratiobetweenthegasphaseconcentration of
aspeciesanditsaqueousphaseconcentration :

Inchemicalengineeringandenvironmentalchemistry,thisdimensionlessconstantisoftencalledtheairwater
partitioningcoefficient .

ValuesofHenry'slawconstants
AlargecompilationofHenry'slawconstantshasbeenpublishedbySander(2015).[2]Afewselectedvaluesare
showninthetablebelow:
Henry'slawconstants(gasesinwaterat298.15K)

equation:

unit: (dimensionless)

O2 770 1.3 103 4.3 104 3.2 102


H2 1300 7.8 104 7.1 104 1.9 102
CO2 29 3.4 102 1.6 103 8.3 101
N2 1600 6.1 104 9.1 104 1.5 102
He 2700 3.7 104 1.5 105 9.1 103
Ne 2200 4.5 104 1.2 105 1.1 102
Ar 710 1.4 103 4.0 104 3.4 102
CO 1100 9.5 104 5.8 104 2.3 102

Temperaturedependence
Whenthetemperatureofasystemchanges,theHenryconstantalsochanges.Thetemperaturedependenceof
equilibriumconstantscangenerallybedescribedwiththevan'tHoffequation,whichalsoappliestoHenry's
lawconstants:

where istheenthalpyofdissolution.Notethattheletter inthesymbol referstoenthalpyand


isnotrelatedtotheletter forHenry'slawconstants.Integratingtheaboveequationandcreatingan
expressionbasedon atthereferencetemperature =298.15Kyields:

Thevan'tHoffequationinthisformisonlyvalidforalimitedtemperaturerangeinwhich doesnot
changemuchwithtemperature.

Thefollowingtablelistssometemperaturedependencies:

Valuesof (inK)
O2 H2 CO2 N2 He Ne Ar CO
1700 500 2400 1300 230 490 1300 1300

Solubilityofpermanentgasesusuallydecreaseswithincreasingtemperatureataroundroomtemperature.
However,foraqueoussolutions,theHenry'slawsolubilityconstantformanyspeciesgoesthroughaminimum.
Formostpermanentgases,theminimumisbelow120C.Often,thesmallerthegasmolecule(andthelower
thegassolubilityinwater),thelowerthetemperatureofthemaximumoftheHenry'slawconstant.Thus,the
maximumisatabout30Cforhelium,92to93Cforargon,nitrogenandoxygen,and114Cforxenon.[7]

EffectiveHenry'slawconstants
TheHenry'slawconstantsmentionedsofardonotconsideranychemicalequilibriaintheaqueousphase.This
typeiscalledthe"intrinsic"(or"physical")Henry'slawconstant.Forexample,theintrinsicHenry'slaw
solubilityconstantofmethanalcanbedefinedas

Inaqueoussolution,methanalisalmostcompletelyhydrated:

Thetotalconcentrationofdissolvedmethanalis

Takingthisequilibriumintoaccount,aneffectiveHenry'slawconstant canbedefinedas

Foracidsandbases,theeffectiveHenry'slawconstantisnotausefulquantitybecauseitdependsonthepHof
thesolution.InordertoobtainapHindependentconstant,theproductoftheintrinsicHenry'slawconstant
andtheacidityconstant isoftenusedforstrongacidslikehydrochloricacid(HCl):

Although isusuallyalsocalledaHenry'slawconstant,itshouldbenotedthatitisadifferentquantityandit
hasdifferentunitsthan .

Dependenceonionicstrength(Sechenovequation)
ValuesofHenry'slawconstantsforaqueoussolutionsdependonthecompositionofthesolution,i.e.,onits
ionicstrengthandondissolvedorganics.Ingeneral,thesolubilityofagasdecreaseswithincreasingsalinity
("saltingout").However,a"saltingin"effecthasalsobeenobserved,forexamplefortheeffectiveHenry'slaw
constantofglyoxal.TheeffectcanbedescribedwiththeSechenovequation,namedaftertheRussian
physiologistIvanSechenov(sometimestheGermantransliteration"Setschenow"oftheCyrillicname
isused).TherearemanyalternativewaystodefinetheSechenovequation,dependingonhowtheaqueous
phasecompositionisdescribed(basedonconcentration,molality,ormolarfraction)andwhichvariantofthe
Henry'slawconstantisused.Describingthesolutionintermsofmolalityispreferredbecausemolalityis
invarianttotemperatureandtotheadditionofdrysalttothesolution.Thus,theSechenovequationcanbe
writtenas

where istheHenry'slawconstantinpurewater, istheHenry'slawconstantinthesaltsolution, is


themolalitybasedSechenovconstant,and isthemolalityofthesalt.

Nonidealsolutions
Henry'slawhasbeenshowntoapplytoawiderangeofsolutesinthelimitof"infinitedilution"(x0),
includingnonvolatilesubstancessuchassucrose.Inthesecases,itisnecessarytostatethelawintermsof
chemicalpotentials.Forasoluteinanidealdilutesolution,thechemicalpotentialdependsonlyonthe
concentration.Fornonidealsolutions,theactivitycoefficientsofthecomponentsmustbetakenintoaccount:

where foravolatilesolutec=1mol/L.

Fornonidealsolutions,theactivitycoefficientcdependsontheconcentrationandmustbedeterminedatthe
concentrationofinterest.Theactivitycoefficientcanalsobeobtainedfornonvolatilesolutes,wherethevapor
pressureofthepuresubstanceisnegligible,byusingtheGibbsDuhemrelation:

Bymeasuringthechangeinvaporpressure(andhencechemicalpotential)ofthesolvent,thechemical
potentialofthesolutecanbededuced.

Thestandardstateforadilutesolutionisalsodefinedintermsofinfinitedilutionbehavior.Althoughthe
standardconcentrationcistakentobe1mol/lbyconvention,thestandardstateisahypotheticalsolutionof
1mol/linwhichthesolutehasitslimitinginfinitedilutionproperties.Thishastheeffectthatallnonideal
behaviorisdescribedbytheactivitycoefficient:theactivitycoefficientat1mol/lisnotnecessarilyunity(and
isfrequentlyquitedifferentfromunity).

Alltherelationsabovecanalsobeexpressedintermsofmolalitiesbratherthanconcentrations,e.g.:

where foravolatilesoluteb=1mol/kg.

Thestandardchemicalpotentialm,theactivitycoefficientmandtheHenry'slawconstantKH,ballhave
differentnumericalvalueswhenmolalitiesareusedinplaceofconcentrations.

Solventmixtures

HenrylawconstantH2,Mforagas2inamixtureofsolvents1and3isrelatedtotheconstantsforindividual
solventsH21andH23:

wherea13istheinteractionparameterofthesolventsfromWohlexpansionoftheexcesschemicalpotentialof
theternarymixtures.

Miscellaneous
Ingeochemistry
Ingeochemistry,aversionofHenry'slawappliestothesolubilityofanoblegasincontactwithsilicatemelt.
Oneequationusedis

where

Cisthenumberconcentrationsofthesolutegasinthemeltandgasphases,
=1/kBT,aninversetemperatureparameter(kBistheBoltzmannconstant),
Eistheexcesschemicalpotentialsofthesolutegasinthetwophases.

ComparisontoRaoult'slaw

Henry'slawisalimitinglawthatonlyappliesfor"sufficientlydilute"solutions.Therangeofconcentrationsin
whichitappliesbecomesnarrowerthemorethesystemdivergesfromidealbehavior.Roughlyspeaking,thatis
themorechemically"different"thesoluteisfromthesolvent.

Foradilutesolution,theconcentrationofthesoluteisapproximatelyproportionaltoitsmolefractionx,and
Henry'slawcanbewrittenas

ThiscanbecomparedwithRaoult'slaw:

wherep*isthevaporpressureofthepurecomponent.

Atfirstsight,Raoult'slawappearstobeaspecialcaseofHenry'slaw,whereKH=p*.Thisistrueforpairsof
closelyrelatedsubstances,suchasbenzeneandtoluene,whichobeyRaoult'slawovertheentirecomposition
range:suchmixturesarecalled"idealmixtures".

Thegeneralcaseisthatbothlawsarelimitlaws,andtheyapplyatoppositeendsofthecompositionrange.The
vaporpressureofthecomponentinlargeexcess,suchasthesolventforadilutesolution,isproportionaltoits
molefraction,andtheconstantofproportionalityisthevaporpressureofthepuresubstance(Raoult'slaw).The
vaporpressureofthesoluteisalsoproportionaltothesolute'smolefraction,buttheconstantofproportionality
isdifferentandmustbedeterminedexperimentally(Henry'slaw).Inmathematicalterms:

Raoult'slaw:

Henry'slaw:

Raoult'slawcanalsoberelatedtonongassolutes.

Seealso
Pervaporation
Partitioncoefficient
Sieverts'law
Graham'slaw
Henryadsorptionconstant

References
1.Henry,W.(1803)."Experimentsonthequantityofgasesabsorbedbywater,atdifferenttemperatures,andunder
differentpressures".Phil.Trans.R.Soc.Lond.93:29274.doi:10.1098/rstl.1803.0004.
2.Sander,R.(2015),"CompilationofHenry'slawconstants(version4.0)forwaterassolvent",Atmos.Chem.Phys.,
15:43994981,Bibcode:2015ACP....15.4399S,doi:10.5194/acp1543992015
3.Sander,R.(1999)."Modelingatmosphericchemistry:Interactionsbetweengasphasespeciesandliquidcloud/aerosol
particles"(review).Surv.Geophys.20:131.Retrieved21March2016.
4.Battino,R.Rettich,T.R.Tominaga,T.(1984)."Thesolubilityofnitrogenandairinliquids".J.Phys.Chem.Ref.
Data.13:563600.
5.Sazonov,VP&Shaw,DG(2006)."IntroductiontotheSolubilityDataSeries:1.5.2.PhysicochemicalQuantities
andUnits,Anoteonnomenclature,points10and11".IntroductiontoIUPACNISTSolubilitiesDatabase.nist.gov.
Retrieved21March2016.
6.Gamsjger,H.Lorimer,J.W.Salomon,M.Shaw,D.G.Tomkins,R.P.T.(2010)."TheIUPACNISTSolubility
DataSeries:Aguidetopreparationanduseofcompilationsandevaluations(IUPACTechnicalReport)".PureAppl.
Chem.82:11371159.doi:10.1351/pacrep091033.
7.Cohen,P.,ed.(1989).TheASMEHandbookonWaterTechnologyforThermalPowerSystems.TheAmericanSociety
ofMechanicalEngineers.p.442.ISBN9780791806340.

Externallinks
EPAOnlineToolsforSiteAssessmentCalculationHenry'slawconversion(https://www3.epa.gov/cea
mpubl/learn2model/parttwo/onsite/henryslaw.html)

Retrievedfrom"https://en.wikipedia.org/w/index.php?title=Henry%27s_law&oldid=765389157"

Categories: Physicalchemistry Equilibriumchemistry Engineeringthermodynamics Gaslaws


Underwaterdivingphysics

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Surfacetension
FromWikipedia,thefreeencyclopedia

Surfacetensionistheelastictendencyofafluidsurfacewhichmakesit
acquiretheleastsurfaceareapossible.Surfacetensionallowsinsects
(e.g.waterstriders),usuallydenserthanwater,tofloatandstrideona
watersurface.

Atliquidairinterfaces,surfacetensionresultsfromthegreater
attractionofliquidmoleculestoeachother(duetocohesion)thantothe
moleculesintheair(duetoadhesion).Theneteffectisaninwardforce
atitssurfacethatcausestheliquidtobehaveasifitssurfacewere
coveredwithastretchedelasticmembrane.Thus,thesurfacebecomes
Surfacetensionandhydrophobicity
undertensionfromtheimbalancedforces,whichisprobablywherethe
interactinthisattempttocutawater
term"surfacetension"camefrom.[1]Becauseoftherelativelyhigh droplet.
attractionofwatermoleculesforeachotherthroughawebofhydrogen
bonds,waterhasahighersurfacetension(72.8millinewtonspermeter
at20C)comparedtothatofmostotherliquids.Surfacetensionisan
importantfactorinthephenomenonofcapillarity.

Surfacetensionhasthedimensionofforceperunitlength,orofenergy
perunitarea.Thetwoareequivalent,butwhenreferringtoenergyper
unitofarea,itiscommontousethetermsurfaceenergy,whichisa
moregeneralterminthesensethatitappliesalsotosolids.
Surfacetensionexperimental
Inmaterialsscience,surfacetensionisusedforeithersurfacestressor demonstrationwithsoap
surfacefreeenergy.

Contents
1 Causes
2 Effectsofsurfacetension
2.1 Water
2.2 Surfactants
3 Physics
3.1 Physicalunits
3.2 Surfaceareagrowth
3.3 Surfacecurvatureandpressure
3.4 Floatingobjects
3.5 Liquidsurface
3.6 Contactangles
3.6.1 Specialcontactangles
4 Methodsofmeasurement
5 Effects
5.1 Liquidinaverticaltube
5.2 Puddlesonasurface
5.3 Thebreakupofstreamsintodrops
6 Thermodynamics
6.1 Thermodynamictheoriesofsurfacetension
6.2 Thermodynamicsofsoapbubbles
6.2.1 Influenceoftemperature
6.2.2 Influenceofsoluteconcentration
6.2.3 Influenceofparticlesizeonvaporpressure
7 Surfacetensionofwaterandofseawater
7.1 Surfacetensionofwater
7.2 Surfacetensionofseawater
8 Datatable
9 Seealso
10 Galleryofeffects
11 Notes
12 References
13 Externallinks

Causes
Thecohesiveforcesamongliquidmoleculesareresponsibleforthe
phenomenonofsurfacetension.Inthebulkoftheliquid,eachmolecule
ispulledequallyineverydirectionbyneighboringliquidmolecules,
resultinginanetforceofzero.Themoleculesatthesurfacedonothave
thesamemoleculesonallsidesofthemandthereforearepulled
inwards.Thiscreatessomeinternalpressureandforcesliquidsurfaces
tocontracttotheminimalarea.

Surfacetensionisresponsiblefortheshapeofliquiddroplets.Although
easilydeformed,dropletsofwatertendtobepulledintoaspherical
shapebytheimbalanceincohesiveforcesofthesurfacelayer.Inthe
absenceofotherforces,includinggravity,dropsofvirtuallyallliquids
wouldbeapproximatelyspherical.Thesphericalshapeminimizesthe
Diagramoftheforcesonmolecules necessary"walltension"ofthesurfacelayeraccordingtoLaplace'slaw.
ofaliquid
Anotherwaytoviewsurface
tensionisintermsofenergy.Amoleculeincontactwithaneighboris
inalowerstateofenergythanifitwerealone(notincontactwitha
neighbor).Theinteriormoleculeshaveasmanyneighborsastheycan
possiblyhave,buttheboundarymoleculesaremissingneighbors
(comparedtointeriormolecules)andthereforehaveahigherenergy.
Fortheliquidtominimizeitsenergystate,thenumberofhigherenergy
boundarymoleculesmustbeminimized.Theminimizedquantityof
boundarymoleculesresultsinaminimalsurfacearea.[2]Asaresultof
surfaceareaminimization,asurfacewillassumethesmoothestshapeit
Waterdropletlyingonadamask.
can(mathematicalproofthat"smooth"shapesminimizesurfacearea
Surfacetensionisbigenoughto
reliesonuseoftheEulerLagrangeequation).Sinceanycurvaturein
preventfloatingbelowthetextile
thesurfaceshaperesultsingreaterarea,ahigherenergywillalsoresult.
Consequently,thesurfacewillpushbackagainstanycurvatureinmuch
thesamewayasaballpusheduphillwillpushbacktominimizeitsgravitationalpotentialenergy.

Effectsofsurfacetension
Water

Severaleffectsofsurfacetensioncanbeseenwithordinarywater:

A.Beadingofrainwateronawaxysurface,suchasaleaf.Wateradheresweaklytowaxandstronglyto
itself,sowaterclustersintodrops.Surfacetensiongivesthemtheirnearsphericalshape,becausea
spherehasthesmallestpossiblesurfaceareatovolumeratio.
B.Formationofdropsoccurswhenamassofliquidisstretched.Theanimationshowswateradheringtothe
faucetgainingmassuntilitisstretchedtoapointwherethesurfacetensioncannolongerkeepthedrop
linkedtothefaucet.Itthenseparatesandsurfacetensionformsthedropintoasphere.Ifastreamof
waterwasrunningfromthefaucet,thestreamwouldbreakupintodropsduringitsfall.Gravitystretches
thestream,thensurfacetensionpinchesitintospheres.[3]
C.Flotationofobjectsdenserthanwateroccurswhentheobjectisnonwettableanditsweightissmall
enoughtobebornebytheforcesarisingfromsurfacetension.[2]Forexample,waterstridersusesurface
tensiontowalkonthesurfaceofapondbythefollowingway.Nonwettabilityoflegofthewaterstrider
meansnoattractionbetweenmoleculesofthelegandmoleculesofthewater,sowhenthelegpushes
downthewater,thesurfacetensionofthewateronlytriestorecoveritsflatnessfromitsdeformationdue
totheleg.Thisbehaviorofthewaterpushthewaterstriderupwardsoitcanstandonthesurfaceofthe
wateraslongasitsmassissmallenoughsothatthewatercansupportit.Thesurfaceofthewater
behaveslikeanelasticfilm:theinsect'sfeetcauseindentationsinthewater'ssurface,increasingits
surfacearea[4]andtendencyofminimizationofsurfacecurvature(soarea)ofthewaterpushesthe
insect'sfeetupward.
D.Separationofoilandwater(inthiscase,waterandliquidwax)iscausedbyatensioninthesurface
betweendissimilarliquids.Thistypeofsurfacetensioniscalled"interfacetension",butitschemistryis
thesame.
E.Tearsofwineistheformationofdropsandrivuletsonthesideofaglasscontaininganalcoholic
beverage.Itscauseisacomplexinteractionbetweenthedifferingsurfacetensionsofwaterandethanol
itisinducedbyacombinationofsurfacetensionmodificationofwaterbyethanoltogetherwithethanol
evaporatingfasterthanwater.

A.Waterbeadingona B.Water C.Waterstridersstay D.Lava E.Photo


leaf dripping atoptheliquid lampwith showing
fromatap becauseofsurface interaction the"tears
tension between ofwine"
dissimilar phenomen
liquids: on.
waterand
liquidwax

Surfactants

Surfacetensionisvisibleinothercommonphenomena,especiallywhensurfactantsareusedtodecreaseit:

Soapbubbleshaveverylargesurfaceareaswithverylittlemass.Bubblesinpurewaterareunstable.The
additionofsurfactants,however,canhaveastabilizingeffectonthebubbles(seeMarangonieffect).
Notethatsurfactantsactuallyreducethesurfacetensionofwaterbyafactorofthreeormore.
Emulsionsareatypeofcolloidinwhichsurfacetensionplaysarole.Tinyfragmentsofoilsuspendedin
purewaterwillspontaneouslyassemblethemselvesintomuchlargermasses.Butthepresenceofa
surfactantprovidesadecreaseinsurfacetension,whichpermitsstabilityofminutedropletsofoilinthe
bulkofwater(orviceversa).

Physics
Physicalunits
Surfacetension,usuallyrepresentedbythesymbol,ismeasuredinforceperunitlength.ItsSIunitisnewton
permeterbutthecgsunitofdynepercentimeterisalsoused.[5]

Surfaceareagrowth

Surfacetensioncanbedefinedintermsofforceorenergy.

Intermsofforce:surfacetensionofaliquidistheforceperunit
length.Intheillustrationontheright,therectangularframe,composed
ofthreeunmovablesides(black)thatforma"U"shape,andafourth
movableside(blue)thatcanslidetotheright.Surfacetensionwillpull
thebluebartothelefttheforceFrequiredtoholdimmobilethe
movablesideisproportionaltothelengthLofthemovableside.Thus
F Thisdiagramillustratestheforce
theratio dependsonlyontheintrinsicpropertiesoftheliquid necessarytoincreasethesurfacearea.
L
(composition,temperature,etc.),notonitsgeometry.Forexample,if Thisforceisproportionaltothe
F surfacetension.
theframehadamorecomplicatedshape,theratio ,withLthelength
L
ofthemovablesideandFtheforcerequiredtostopitfromsliding,is
foundtobethesameforallshapes.Wethereforedefinethesurfacetensionas

Thereasonforthe 12 isthatthefilmhastwosides,eachofwhichcontributesequallytotheforcesotheforce
F
contributedbyasinglesideisL= 2 .

Intermsofenergy:surfacetensionofaliquidistheratioofthechangeintheenergyoftheliquid,andthe
changeinthesurfaceareaoftheliquid(thatledtothechangeinenergy).Thiscanbeeasilyrelatedtothe
previousdefinitionintermsofforce:[6]ifFistheforcerequiredtostopthesidefromstartingtoslide,thenthis
isalsotheforcethatwouldkeepthesideinthestateofslidingataconstantspeed(byNewton'sSecondLaw).
Butifthesideismovingtotheright(inthedirectiontheforceisapplied),thenthesurfaceareaofthestretched
liquidisincreasingwhiletheappliedforceisdoingworkontheliquid.Thismeansthatincreasingthesurface
areaincreasestheenergyofthefilm.TheworkdonebytheforceFinmovingthesidebydistancexis
W=FxatthesametimethetotalareaofthefilmincreasesbyA=2Lx(thefactorof2isherebecause
1F
theliquidhastwosides,twosurfaces).Thus,multiplyingboththenumeratorandthedenominatorof=
2L
byx,weget

ThisworkWis,bytheusualarguments,interpretedasbeingstoredaspotentialenergy.Consequently,surface
tensioncanbealsomeasuredinSIsystemasjoulespersquaremeterandinthecgssystemasergspercm2.
Sincemechanicalsystemstrytofindastateofminimumpotentialenergy,afreedropletofliquidnaturally
assumesasphericalshape,whichhastheminimumsurfaceareaforagivenvolume.Theequivalenceof
measurementofenergyperunitareatoforceperunitlengthcanbeprovenbydimensionalanalysis.[7]

Surfacecurvatureandpressure
Ifnoforceactsnormaltoatensionedsurface,thesurfacemustremain
flat.Butifthepressureononesideofthesurfacediffersfrompressure
ontheotherside,thepressuredifferencetimessurfacearearesultsina
normalforce.Inorderforthesurfacetensionforcestocanceltheforce
duetopressure,thesurfacemustbecurved.Thediagramshowshow
surfacecurvatureofatinypatchofsurfaceleadstoanetcomponentof
surfacetensionforcesactingnormaltothecenterofthepatch.Whenall Surfacetensionforcesactingona
theforcesarebalanced,theresultingequationisknownastheYoung tiny(differential)patchofsurface.
Laplaceequation:[8] xandyindicatetheamountof
bendoverthedimensionsofthe
patch.Balancingthetensionforces
withpressureleadstotheYoung
Laplaceequation
where:

pisthepressuredifference,knownastheLaplacepressure.[9]
issurfacetension.
RxandRyareradiiofcurvatureineachoftheaxesthatareparalleltothesurface.

Thequantityinparenthesesontherighthandsideisinfact(twice)themeancurvatureofthesurface
(dependingonnormalisation).Solutionstothisequationdeterminetheshapeofwaterdrops,puddles,menisci,
soapbubbles,andallothershapesdeterminedbysurfacetension(suchastheshapeoftheimpressionsthata
waterstrider'sfeetmakeonthesurfaceofapond).Thetablebelowshowshowtheinternalpressureofawater
dropletincreaseswithdecreasingradius.Fornotverysmalldropstheeffectissubtle,butthepressure
differencebecomesenormouswhenthedropsizesapproachthemolecularsize.(Inthelimitofasingle
moleculetheconceptbecomesmeaningless.)

pforwaterdropsofdifferentradiiatSTP
Dropletradius 1mm 0.1mm 1m 10nm
p(atm) 0.0014 0.0144 1.436 143.6

Floatingobjects

Whenanobjectisplacedonaliquid,itsweightFwdepressesthe
surface,andifsurfacetensionanddownwardforcebecomesequalthan
isbalancedbythesurfacetensionforcesoneithersideFs,whichare
eachparalleltothewater'ssurfaceatthepointswhereitcontactsthe
object.Noticethatsmallmomentinthebodymaycausetheobjectsink
astheangleofcontactdecreasessurfacetensiondecreasesthe
horizontalcomponentsofthetwoFsarrowspointinopposite Crosssectionofaneedlefloatingon
directions,sotheycanceleachother,buttheverticalcomponentspoint thesurfaceofwater. Fwistheweight
inthesamedirectionandthereforeaddup[2]tobalanceFw.Theobject's and Fsaresurfacetensionresultant
surfacemustnotbewettableforthistohappen,anditsweightmustbe forces.
lowenoughforthesurfacetensiontosupportit.

Liquidsurface

Tofindtheshapeoftheminimalsurfaceboundedbysomearbitraryshapedframeusingstrictlymathematical
meanscanbeadauntingtask.Yetbyfashioningtheframeoutofwireanddippingitinsoapsolution,alocally
minimalsurfacewillappearintheresultingsoapfilmwithinseconds.[7][10]
Thereasonforthisisthatthepressuredifferenceacrossafluidinterface
isproportionaltothemeancurvature,asseenintheYoungLaplace
equation.Foranopensoapfilm,thepressuredifferenceiszero,hence
themeancurvatureiszero,andminimalsurfaceshavethepropertyof
zeromeancurvature.

Minimalsurface

Contactangles

Thesurfaceofanyliquidisaninterfacebetweenthatliquidandsomeothermedium.[note1]Thetopsurfaceofa
pond,forexample,isaninterfacebetweenthepondwaterandtheair.Surfacetension,then,isnotapropertyof
theliquidalone,butapropertyoftheliquid'sinterfacewithanothermedium.Ifaliquidisinacontainer,then
besidestheliquid/airinterfaceatitstopsurface,thereisalsoaninterfacebetweentheliquidandthewallsof
thecontainer.Thesurfacetensionbetweentheliquidandairisusuallydifferent(greaterthan)itssurface
tensionwiththewallsofacontainer.Andwherethetwosurfacesmeet,theirgeometrymustbesuchthatall
forcesbalance.[7][8]

Wherethetwosurfacesmeet,theyformacontactangle,,which
istheanglethetangenttothesurfacemakeswiththesolid
surface.Thediagramtotherightshowstwoexamples.Tension
forcesareshownfortheliquidairinterface,theliquidsolid
interface,andthesolidairinterface.Theexampleontheleftis
wherethedifferencebetweentheliquidsolidandsolidair
surfacetension,lssa,islessthantheliquidairsurface
tension,la,butisneverthelesspositive,thatis

Inthediagram,boththeverticalandhorizontalforcesmust Forcesatcontactpointshownforcontact
cancelexactlyatthecontactpoint,knownasequilibrium.The anglegreaterthan90(left)andlessthan
horizontalcomponentofflaiscanceledbytheadhesiveforce, 90(right)
fA.[7]

Themoretellingbalanceofforces,though,isintheverticaldirection.Theverticalcomponentofflamust
exactlycanceltheforce,fls.[7]

Sincetheforcesareindirectproportiontotheir Liquid Solid Contactangle


respectivesurfacetensions,wealsohave:[8] water
ethanol
sodalimeglass
diethylether
leadglass 0
carbontetrachloride fusedquartz
where
glycerol
lsistheliquidsolidsurfacetension, aceticacid
laistheliquidairsurfacetension, water paraffinwax 107

isthesolidairsurfacetension,
saisthesolidairsurfacetension, silver 90
isthecontactangle,whereaconcavemeniscus sodalimeglass 29
hascontactanglelessthan90andaconvex methyliodide leadglass 30
meniscushascontactangleofgreaterthan90.[7] fusedquartz 33
mercury sodalimeglass 140
Thismeansthatalthoughthedifferencebetweenthe
Someliquidsolidcontactangles[7]
liquidsolidandsolidairsurfacetension,lssa,is
difficulttomeasuredirectly,itcanbeinferredfromthe
liquidairsurfacetension,la,andtheequilibriumcontactangle,,whichisafunctionoftheeasily
measurableadvancingandrecedingcontactangles(seemainarticlecontactangle).

Thissamerelationshipexistsinthediagramontheright.Butinthiscaseweseethatbecausethecontactangle
islessthan90,theliquidsolid/solidairsurfacetensiondifferencemustbenegative:

Specialcontactangles

Observethatinthespecialcaseofawatersilverinterfacewherethecontactangleisequalto90,theliquid
solid/solidairsurfacetensiondifferenceisexactlyzero.

Anotherspecialcaseiswherethecontactangleisexactly180.WaterwithspeciallypreparedTeflon
approachesthis.[8]Contactangleof180occurswhentheliquidsolidsurfacetensionisexactlyequaltothe
liquidairsurfacetension.

Methodsofmeasurement
Becausesurfacetensionmanifestsitselfinvariouseffects,itoffersa
numberofpathstoitsmeasurement.Whichmethodisoptimaldepends
uponthenatureoftheliquidbeingmeasured,theconditionsunder
whichitstensionistobemeasured,andthestabilityofitssurfacewhen
itisdeformed.

DuNoyringmethod:Thetraditionalmethodusedtomeasure
surfaceorinterfacialtension.Wettingpropertiesofthesurfaceor
interfacehavelittleinfluenceonthismeasuringtechnique.
Maximumpullexertedontheringbythesurfaceismeasured.[11]
DuNoyPaddaymethod:AminimizedversionofDuNoy Surfacetensioncanbemeasured
methodusesasmalldiametermetalneedleinsteadofaring,in usingthependantdropmethodona
combinationwithahighsensitivitymicrobalancetorecord goniometer.
maximumpull.Theadvantageofthismethodisthatverysmall
samplevolumes(downtofewtensofmicroliters)canbemeasuredwithveryhighprecision,withoutthe
needtocorrectforbuoyancy(foraneedleorrather,rod,withpropergeometry).Further,the
measurementcanbeperformedveryquickly,minimallyinabout20seconds.Firstcommercial
multichanneltensiometers[CMCeeker]wererecentlybuiltbasedonthisprinciple.
Wilhelmyplatemethod:Auniversalmethodespeciallysuitedtochecksurfacetensionoverlongtime
intervals.Averticalplateofknownperimeterisattachedtoabalance,andtheforceduetowettingis
measured.[12]
Spinningdropmethod:Thistechniqueisidealformeasuringlowinterfacialtensions.Thediameterofa
dropwithinaheavyphaseismeasuredwhilebotharerotated.
Pendantdropmethod:Surfaceandinterfacialtensioncanbemeasuredbythistechnique,evenatelevated
temperaturesandpressures.Geometryofadropisanalyzedoptically.Forpendantdropsthemaximum
diameterandtheratiobetweenthisparameterandthediameteratthedistanceofthemaximumdiameter
fromthedropapexhasbeenusedtoevaluatethesizeandshapeparametersinordertodeterminesurface
tension.
Bubblepressuremethod(Jaeger'smethod):Ameasurementtechniquefordeterminingsurfacetensionat
shortsurfaceages.Maximumpressureofeachbubbleismeasured.
Dropvolumemethod:Amethodfordetermininginterfacialtensionasafunctionofinterfaceage.Liquid
ofonedensityispumpedintoasecondliquidofadifferentdensityandtimebetweendropsproducedis
measured.[13]
Capillaryrisemethod:Theendofacapillaryisimmersedintothesolution.Theheightatwhichthe
solutionreachesinsidethecapillaryisrelatedtothesurfacetensionbytheequationdiscussedbelow.[14]
Stalagmometricmethod:Amethodofweightingandreadingadropofliquid.
Sessiledropmethod:Amethodfordeterminingsurfacetensionanddensitybyplacingadropona
substrateandmeasuringthecontactangle(seeSessiledroptechnique).[15]
Vibrationalfrequencyoflevitateddrops:Thenaturalfrequencyofvibrationaloscillationsofmagnetically
levitateddropshasbeenusedtomeasurethesurfacetensionofsuperfluid4He.Thisvalueisestimatedto
be0.375dyn/cmatT=0K.[16]
Resonantoscillationsofsphericalandhemisphericalliquiddrop:Thetechniqueisbasedonmeasuring
theresonantfrequencyofsphericalandhemisphericalpendantdropletsdriveninoscillationsbya
modulatedelectricfield.Thesurfacetensionandviscositycanbeevaluatedfromtheobtainedresonant
curves.[17][18][19]

Effects
Liquidinaverticaltube

Anoldstylemercurybarometerconsistsofaverticalglasstubeabout1cmin
diameterpartiallyfilledwithmercury,andwithavacuum(calledTorricelli's
vacuum)intheunfilledvolume(seediagramtotheright).Noticethatthe
mercurylevelatthecenterofthetubeishigherthanattheedges,makingthe
uppersurfaceofthemercurydomeshaped.Thecenterofmassoftheentire
columnofmercurywouldbeslightlylowerifthetopsurfaceofthemercury
wereflatovertheentirecrosssectionofthetube.Butthedomeshapedtopgives
slightlylesssurfaceareatotheentiremassofmercury.Againthetwoeffects
combinetominimizethetotalpotentialenergy.Suchasurfaceshapeisknownas
aconvexmeniscus.

Weconsiderthesurfaceareaoftheentiremassofmercury,includingthepartof
thesurfacethatisincontactwiththeglass,becausemercurydoesnotadhereto
glassatall.Sothesurfacetensionofthemercuryactsoveritsentiresurfacearea,
includingwhereitisincontactwiththeglass.Ifinsteadofglass,thetubewas
madeoutofcopper,thesituationwouldbeverydifferent.Mercuryaggressively
adherestocopper.Soinacoppertube,thelevelofmercuryatthecenterofthe
tubewillbelowerthanattheedges(thatis,itwouldbeaconcavemeniscus).In Diagramofamercury
asituationwheretheliquidadherestothewallsofitscontainer,weconsiderthe barometer
partofthefluid'ssurfaceareathatisincontactwiththecontainertohave
negativesurfacetension.Thefluidthenworkstomaximizethecontactsurfacearea.Sointhiscaseincreasing
theareaincontactwiththecontainerdecreasesratherthanincreasesthepotentialenergy.Thatdecreaseis
enoughtocompensatefortheincreasedpotentialenergyassociatedwithliftingthefluidnearthewallsofthe
container.

Ifatubeissufficientlynarrowandtheliquidadhesiontoitswallsissufficientlystrong,surfacetensioncan
drawliquidupthetubeinaphenomenonknownascapillaryaction.Theheighttowhichthecolumnisliftedis
givenby:[7]
where

histheheighttheliquidislifted,
laistheliquidairsurfacetension,
isthedensityoftheliquid,
ristheradiusofthecapillary,
gistheaccelerationduetogravity,
istheangleofcontactdescribedabove.Ifisgreaterthan90,
aswithmercuryinaglasscontainer,theliquidwillbedepressed
ratherthanlifted.

Illustrationofcapillaryriseandfall.
Red=contactanglelessthan90
blue=contactanglegreaterthan90

Puddlesonasurface

Pouringmercuryontoahorizontalflatsheetofglassresults
inapuddlethathasaperceptiblethickness.Thepuddlewill
spreadoutonlytothepointwhereitisalittleunderhalfa
centimetrethick,andnothinner.Againthisisduetothe
actionofmercury'sstrongsurfacetension.Theliquidmass
flattensoutbecausethatbringsasmuchofthemercuryto
aslowalevelaspossible,butthesurfacetension,atthe
sametime,isactingtoreducethetotalsurfacearea.The
resultofthecompromiseisapuddleofanearlyfixed
thickness.

Thesamesurfacetensiondemonstrationcanbedonewith Profilecurveoftheedgeofapuddlewherethe
water,limewaterorevensaline,butonlyonasurfacemade contactangleis180.Thecurveisgivenbythe
ofasubstancetowhichwaterdoesnotadhere.Waxissuch formula:[8]
asubstance.Waterpouredontoasmooth,flat,horizontal
waxsurface,sayawaxedsheetofglass,willbehave
similarlytothemercurypouredontoglass.
where
Thethicknessofapuddleofliquidonasurfacewhose
contactangleis180isgivenby:[8]

where

histhedepthofthepuddleincentimetersormeters.
isthesurfacetensionoftheliquidindynespercentimeterornewtonspermeter.
gistheaccelerationduetogravityandisequalto980cm/s2or9.8m/s2
isthedensityoftheliquidingramspercubiccentimeteror
isthedensityoftheliquidingramspercubiccentimeteror
kilogramspercubicmeter

Inreality,thethicknessesofthepuddleswillbeslightlylessthanwhat
ispredictedbytheaboveformulabecauseveryfewsurfaceshavea
contactangleof180withanyliquid.Whenthecontactangleisless
than180,thethicknessisgivenby:[8]

Smallpuddlesofwateronasmooth
cleansurfacehaveperceptible
thickness.

Formercuryonglass,Hg=487dyn/cm,Hg=13.5g/cm3and=
140,whichgiveshHg=0.36cm.Forwateronparaffinat25C,=
72dyn/cm,=1.0g/cm3,and=107whichgiveshH O=0.44cm.
2
Illustrationofhowlowercontact
Theformulaalsopredictsthatwhenthecontactangleis0,theliquid angleleadstoreductionofpuddle
willspreadoutintoamicrothinlayeroverthesurface.Suchasurface depth
issaidtobefullywettablebytheliquid.

Thebreakupofstreamsintodrops

Indaytodaylifeallofusobservethatastreamofwateremergingfrom
afaucetwillbreakupintodroplets,nomatterhowsmoothlythestream
isemittedfromthefaucet.Thisisduetoaphenomenoncalledthe
PlateauRayleighinstability,[8]whichisentirelyaconsequenceofthe
effectsofsurfacetension.

Theexplanationofthisinstabilitybeginswiththeexistenceoftiny
perturbationsinthestream.Thesearealwayspresent,nomatterhow
smooththestreamis.Iftheperturbationsareresolvedintosinusoidal
components,wefindthatsomecomponentsgrowwithtimewhile
othersdecaywithtime.Amongthosethatgrowwithtime,somegrowat
fasterratesthanothers.Whetheracomponentdecaysorgrows,andhow
fastitgrowsisentirelyafunctionofitswavenumber(ameasureof
howmanypeaksandtroughspercentimeter)andtheradiiofthe
originalcylindricalstream.

Thermodynamics
Thermodynamictheoriesofsurfacetension Intermediatestageofajetbreaking
intodrops.Radiiofcurvatureinthe
J.W.Gibbsdevelopedthethermodynamictheoryofcapillaritybasedon axialdirectionareshown.Equation
theideaofsurfacesofdiscontinuity.[20]Heintroducedandstudied fortheradiusofthestreamis R(z)=
thermodynamicsoftwodimensionalobjectssurfaces.Thesesurfaces R0+Akcos(kz),whereR0isthe
havearea,mass,entropy,energyandfreeenergy.Asstatedabove,the radiusoftheunperturbedstream, Ak
mechanicalworkneededtoincreaseasurfaceareaAisdW=dA. istheamplitudeoftheperturbation, z
Henceatconstanttemperatureandpressure,surfacetensionequals isdistancealongtheaxisofthe
Gibbsfreeenergypersurfacearea:[8] stream,and kisthewavenumber

whereGisGibbsfreeenergyandAisthearea.
whereGisGibbsfreeenergyandAisthearea.

ThermodynamicsrequiresthatallspontaneouschangesofstateareaccompaniedbyadecreaseinGibbsfree
energy.

Fromthisitiseasytounderstandwhydecreasingthesurfaceareaofamassofliquidisalwaysspontaneous
(G<0),provideditisnotcoupledtoanyotherenergychanges.Itfollowsthatinordertoincreasesurface
area,acertainamountofenergymustbeadded.

Gibbsfreeenergyisdefinedbytheequation[21]G=HTS,whereHisenthalpyandSisentropy.Based
uponthisandthefactthatsurfacetensionisGibbsfreeenergyperunitarea,itispossibletoobtainthe
followingexpressionforentropyperunitarea:

Kelvin'sequationforsurfacesarisesbyrearrangingthepreviousequations.Itstatesthatsurfaceenthalpyor
surfaceenergy(differentfromsurfacefreeenergy)dependsbothonsurfacetensionanditsderivativewith
temperatureatconstantpressurebytherelationship.[22]

FifteenyearsafterGibbs,J.D.vanderWaalsdevelopedthetheoryofcapillarityeffectsbasedonthehypothesis
ofacontinuousvariationofdensity.[23]Headdedtotheenergydensitytheterm wherecisthe
capillaritycoefficientandisthedensity.Forthemultiphaseequilibria,theresultsofthevanderWaals
approachpracticallycoincidewiththeGibbsformulae,butformodellingofthedynamicsofphasetransitions
thevanderWaalsapproachismuchmoreconvenient.[24][25]ThevanderWaalscapillarityenergyisnow
widelyusedinthephasefieldmodelsofmultiphaseflows.Suchtermsarealsodiscoveredinthedynamicsof
nonequilibriumgases.[26]

Thermodynamicsofsoapbubbles

Thepressureinsideanideal(onesurface)soapbubblecanbederivedfromthermodynamicfreeenergy
considerations.Atconstanttemperatureandparticlenumber,dT=dN=0,thedifferentialHelmholtzenergy
isgivenby

wherePisthedifferenceinpressureinsideandoutsideofthebubble,andisthesurfacetension.In
equilibrium,dF=0,andso,

Forasphericalbubble,thevolumeandsurfaceareaaregivensimplyby

and

Substitutingtheserelationsintothepreviousexpression,wefind
whichisequivalenttotheYoungLaplaceequationwhenRx=Ry.Forrealsoapbubbles,thepressureis
doubledduetothepresenceoftwointerfaces,oneinsideandoneoutside.

Influenceoftemperature

Surfacetensionisdependentontemperature.Forthatreason,whena
valueisgivenforthesurfacetensionofaninterface,temperaturemust
beexplicitlystated.Thegeneraltrendisthatsurfacetensiondecreases
withtheincreaseoftemperature,reachingavalueof0atthecritical
temperature.ForfurtherdetailsseeEtvsrule.Thereareonly
empiricalequationstorelatesurfacetensionandtemperature:

Etvs:[11][22][27]

Temperaturedependenceofthe
surfacetensionbetweentheliquidand
HereVisthemolarvolumeofasubstance,TCisthecritical vaporphasesofpurewater
temperatureandkisaconstantvalidforalmostallsubstances.[11]A
2
typicalvalueisk=2.1 107JK1mol 3.[11][27]Forwateronecan
furtheruseV=18ml/molandTC=647K(374C).[28]

AvariantonEtvsisdescribedbyRamayandShields:[21]

wherethetemperatureoffsetof6kelvinsprovidestheformulawitha
betterfittorealityatlowertemperatures.
Temperaturedependencyofthe
GuggenheimKatayama:[22]
surfacetensionofbenzene

isaconstantforeachliquidandnisanempiricalfactor,whosevalueis 11
9 fororganicliquids.Thisequation
wasalsoproposedbyvanderWaals,whofurtherproposedthatcouldbegivenbytheexpression

whereK2isauniversalconstantforallliquids,andPCisthecriticalpressureoftheliquid(althoughlater
experimentsfoundK2tovarytosomedegreefromoneliquidtoanother).[22]

BothGuggenheimKatayamaandEtvstakeintoaccountthefactthatsurfacetensionreaches0atthecritical
temperature,whereasRamayandShieldsfailstomatchrealityatthisendpoint.

Influenceofsoluteconcentration

Solutescanhavedifferenteffectsonsurfacetensiondependingonthenatureofthesurfaceandthesolute:
Littleornoeffect,forexamplesugaratwater|air,mostorganiccompoundsatoil|air
Increasesurfacetension,mostinorganicsaltsatwater|air
Nonmonotonicchange,mostinorganicacidsatwater|air
Decreasesurfacetensionprogressively,aswithmostamphiphiles,e.g.,alcoholsatwater|air
Decreasesurfacetensionuntilcertaincriticalconcentration,andnoeffectafterwards:surfactantsthat
formmicelles

Whatcomplicatestheeffectisthatasolutecanexistinadifferentconcentrationatthesurfaceofasolventthan
initsbulk.Thisdifferencevariesfromonesolutesolventcombinationtoanother.

Gibbsisothermstatesthat:

isknownassurfaceconcentration,itrepresentsexcessofsoluteperunitareaofthesurfaceoverwhat
wouldbepresentifthebulkconcentrationprevailedallthewaytothesurface.Ithasunitsofmol/m2
Cistheconcentrationofthesubstanceinthebulksolution.
RisthegasconstantandTthetemperature
Certainassumptionsaretakeninitsdeduction,thereforeGibbsisothermcanonlybeappliedtoideal(very
dilute)solutionswithtwocomponents.

Influenceofparticlesizeonvaporpressure

TheClausiusClapeyronrelationleadstoanotherequationalsoattributedtoKelvin,astheKelvinequation.It
explainswhy,becauseofsurfacetension,thevaporpressureforsmalldropletsofliquidinsuspensionisgreater
thanstandardvaporpressureofthatsameliquidwhentheinterfaceisflat.Thatistosaythatwhenaliquidis
formingsmalldroplets,theequilibriumconcentrationofitsvaporinitssurroundingsisgreater.Thisarises
becausethepressureinsidethedropletisgreaterthanoutside.[21]

Pvisthestandardvaporpressureforthatliquidatthat
temperatureandpressure.
Visthemolarvolume.
Risthegasconstant
rkistheKelvinradius,theradiusofthedroplets.

Theeffectexplainssupersaturationofvapors.Intheabsenceof
nucleationsites,tinydropletsmustformbeforetheycanevolveinto
largerdroplets.Thisrequiresavaporpressuremanytimesthevapor Moleculesonthesurfaceofatiny
pressureatthephasetransitionpoint.[21] droplet(left)have,onaverage,fewer
neighborsthanthoseonaflatsurface
Thisequationisalsousedincatalystchemistrytoassessmesoporosity (right).Hencetheyareboundmore
forsolids.[29] weaklytothedropletthanareflat
surfacemolecules.
Theeffectcanbeviewedintermsoftheaveragenumberofmolecular
neighborsofsurfacemolecules(seediagram).

Thetableshowssomecalculatedvaluesofthiseffectforwateratdifferentdropsizes:

P [22]
P0 forwaterdropsofdifferentradiiatSTP
Dropletradius 1000 100 10 1
(nm)
P
P0 1.001 1.011 1.114 2.95

Theeffectbecomesclearforverysmalldropsizes,asadropof1nmradiushasabout100moleculesinside,
whichisaquantitysmallenoughtorequireaquantummechanicsanalysis.

Surfacetensionofwaterandofseawater
ThetwomostabundantliquidsonEartharefreshwaterandseawater.Thissectiongivescorrelationsof
referencedataforthesurfacetensionofboth.

Surfacetensionofwater

ThesurfacetensionofpureliquidwaterincontactwithitsvaporhasbeengivenbyIAPWS[30]as

wherebothTandthecriticaltemperature,TC=647.098K,areexpressedinkelvin.Theregionofvaliditythe
entirevaporliquidsaturationcurve,fromthetriplepoint(0.01C)tothecriticalpoint.Italsoprovides
reasonableresultswhenextrapolatedtometastable(supercooled)conditions,downtoatleast25C.This
formulationwasoriginallyadoptedbyIAPWSin1976,andwasadjustedin1994toconformtothe
InternationalTemperatureScaleof1990.

TheuncertaintyofthisformulationisgivenoverthefullrangeoftemperaturebyIAPWS.[30]Fortemperatures
below100C,theuncertaintyis0.5%.

Surfacetensionofseawater

Nayaretal.[31]publishedreferencedataforthesurfacetensionofseawateroverthesalinityrangeof
20S131g/kgandatemperaturerangeof1t92Catatmosphericpressure.Theuncertaintyofthe
measurementsvariedfrom0.18to0.37mN/mwiththeaverageuncertaintybeing0.22mN/m.Thisdatais
correlatedbythefollowingequation

whereswisthesurfacetensionofseawaterinmN/m,wisthesurfacetensionofwaterinmN/m,Sisthe
referencesalinity[32]ing/kg,andtistemperatureindegreesCelsius.Theaverageabsolutepercentagedeviation
betweenmeasurementsandthecorrelationwas0.19%whilethemaximumdeviationis0.60%.

Therangeoftemperatureandsalinityencompassesboththeoceanographicrangeandtherangeofconditions
encounteredinthermaldesalinationtechnologies.

Datatable
Surfacetensionofvariousliquidsindyn/cmagainstair[33]
Mixturecompositionsdenoted"%"arebymass
dyn/cmisequivalenttotheSIunitsofmN/m(millinewtonpermeter)
Liquid Temperature(C) Surfacetension,
Aceticacid 20 27.60
Aceticacid(40.1%)+Water 30 40.68
Aceticacid(10.0%)+Water 30 54.56
Acetone 20 23.70
Diethylether 20 17.00
Ethanol 20 22.27
Ethanol(40%)+Water 25 29.63
Ethanol(11.1%)+Water 25 46.03
Glycerol 20 63.00
nHexane 20 18.40
Hydrochloricacid17.7Maqueoussolution 20 65.95
Isopropanol 20 21.70
LiquidheliumII 273 [34]0.37

Liquidnitrogen 196 8.85


Mercury 15 487.00
Methanol 20 22.60
nOctane 20 21.80
Sodiumchloride6.0Maqueoussolution 20 82.55
Sucrose(55%)+water 20 76.45
Water 0 75.64
Water 25 71.97
Water 50 67.91
Water 100 58.85
Toluene 25 27.73

Seealso
Antifog DortmundDataBank Meniscussurface
Capillarywaveshort containsexperimental curvatureformedbyaliquid
wavesonawatersurface, temperaturedependent inacontainer
governedbysurfacetension surfacetensions Mercurybeatinghearta
andinertia Electrodippingforce consequenceof
Cheerioeffectthe Electrowetting inhomogeneoussurface
tendencyforsmallwettable Electrocapillarity tension
floatingobjectstoattractone Etvsrulearulefor Microfluidics
another. predictingsurfacetension Sessiledroptechnique
Cohesion dependentontemperature SowHsinChen
Dimensionlessnumbers Fluidpipe Specificsurfaceenergy
Bondnumberor Hydrostaticequilibrium sameassurfacetensionin
Etvsnumber theeffectofgravitypulling isotropicmaterials.
Capillarynumber matterintoaroundshape Spinningdropmethod
Marangoninumber Interface(chemistry) Stalagmometricmethod
Webernumber Surfacepressure
Surfacescience Tearsofwinethesurface Wettinganddewetting
Surfacetensionvalues tensioninducedphenomenon
Surfactantssubstances seenonthesidesofglasses
whichreducesurface containingalcoholic
tension. beverages.
Szyszkowskiequation Tolmanlengthleading
Calculatingsurfacetension termincorrectingthesurface
ofaqueoussolutions tensionforcurvedsurfaces.

Galleryofeffects

Breakupofamovingsheetof Photoofflowingwater Asoapbubblebalances


waterbouncingoffofa adheringtoahand.Surface surfacetensionforcesagainst
spoon. tensioncreatesthesheetof internalpneumaticpressure.
waterbetweentheflowand
thehand.

Surfacetensionpreventsa Adaisy.Theentiretyofthe Ametalpaperclipfloatson


coinfromsinking:thecoinis flowerliesbelowthelevelof water.Severalcanusuallybe
indisputablydenserthan the(undisturbed)free carefullyaddedwithout
water,soitmustbe surface.Thewaterrises overflowofwater.
displacingavolumegreater smoothlyarounditsedge.
thanitsownforbuoyancyto Surfacetensionprevents
balancemass. waterfillingtheairbetween
thepetalsandpossibly
submergingtheflower.

Analuminiumcoinfloatson Ametalpaperclipfloatingon
thesurfaceofthewaterat water.Agrillinfrontofthe
10C.Anyextraweight lighthascreatedthe'contour
woulddropthecointothe lines'whichshowthe
bottom. deformationinthewater
surfacecausedbythemetal
paperclip.

Notes
1.Inamercurybarometer,theupperliquidsurfaceisaninterfacebetweentheliquidandavacuumcontainingsome
moleculesofevaporatedliquid.

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Externallinks
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SurfaceTensionsofVariousLiquids(http://www.kayelaby.npl.co. tension.
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4 ,Na ,K ,Mg ,Ca ,SO4 ,NO3 ,Cl ,CO3 ,Br andOH .

T.ProctorHall(1893)Newmethodsofmeasuringsurfacetensioninliquids(http://biodiversitylibrary.or
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TheBubbleWall(http://www.magnet.fsu.edu/education/community/slideshows/bubblewall/index.html)
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es/basics/)

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