Chapter 1 Characteristic Features of Surfactants 1

1
Chapter 1 Characteristic Featuresof Surfactants

• ???????

2
1?????????

• ??????????????
• 1???????
• (1)???( R??C8-C20)
• (a)??(Alkyl)
• ?????
• ????(???)dodecyl (lauric )
• ????(????)tetradecyl (myristic)
• ????(???)cetyl (palmitic )
• ????(???)octadecyl(stearic )
• CH3-(CH2)n-COOMe

3

• (b)???(Alkenyl)???,????????????????????
• ??,???? ??(9-???? oleic acid),
• CH3(CH2)7CHCH(CH2)7COOMe
• ???(9,12-?????linoleic acid)
• CH3(CH2)4CHCHCH2CHCH(CH2)7COOMe
• ????????
• ???,6?????????????3.5?????CH3(CH2)11-C6H4-SO3Na
  
• RC15.5

4

• (c)???????,??????????????
• ??,????(ricinoleic acid)
• 12-??-9-?????????????

5

• (2) ????????????
• (a) ??????Length of the Hydrophobic Group
• If increase in the length of the hydrophobic
  group then
• ???Decreases the solubility of the surfactant in
  water and increases its solubility in organic
  so1vents,

6

• b)??????Causes closer packing of the surfactant
  molecules at the interface,
• c) ??????????Increases the tendency of the
  surfactant to adsorb at an interface or to form
  micelles,
• d) ????Increases the melting point of the
  surfactant and of the adsorbed film,
• e) ??????????Increases the sensitivity of the
  surfactant, if it is ionic, to precipitation from
  water by counter-ions.

7

• (b) ??????????(Branching and Un-saturation)
• The introduction of branching or
  un-saturation into the hydrophobic group
• ???Increases the solubility of the surfactant in
  water or in organic solvents (compared to the
  straight-chain, saturated isomer),
• ????Decreases the melting point of the
  surfactant and of the adsorbed film.

8

• c)?????????????Causes looser packing of the
  surfactant molecules at the interface and
  inhibits liquid-crystal formation in solution,
• d)???????????May cause oxidation and color
  formation in unsaturated compounds,
• e)????????????May decrease biodegradability in
  branched -chain compounds.

9

• (c) ?????Aromatic Nucleus
• The presence of an aromatic nucleus in the
  hydrophobic group may
• Increase the adsorption of the surfactant onto
  polar surfaces,
• Decrease its biodegradability,
• Cause looser packing of the surfactant molecules
  at the interface. Cycloaliphatic nuclei, such as
  those in rosin derivatives, are even more loose1y
  packed.

10

• (d) ?????Polyoxypropylene Chain H(OC3H6)x-
• The presence of this in the hydrophobic
  group
• Increases adsorption of the surfactant onto polar
  surfaces via the hydrophobic group,
• Increases the solubility of the surfactant in
  organic so1vents.

11

• 2? ???(silane ) ???????(siloxane)?
  ???????????????
• The presence of either of these groups as the
  hydrophobic group in the surfactant permits
  reduction of the surface tension of water to
  lower values that those attainable with a
  hydrocarbon- based hydrophobic group

12

• 3??????????????????????,CF3(CH2)6CH2-
  ?CF3(CF2)6CF2- ???????????,????,?????
• Presence of Partially fluorinated chains and
  Perfluorocarbon chains.
• Perfluoroalkyl groups are both water- and
  hydrocarbon-repel1ent(?????).

13

• 4??????? Hydrophobic Grougs
• (1) Straight-chain, long alkyl groups (C8-C20)
• (2) Branched-chain, long alkyl groups (C8-C20)
• (3) Long-chain (C8-C15) alkylbenzene
  residues(R-C6H4-)
• (4) Alky1naphthalene residues (C3 and
  greater-length alkyl groups)(R-C10H8-)
• (5) Rosin(??) derivatives(???)
• (6) High-molecular-weight propylene oxide
  polymers
• (7) Lignin(???) derivatives
• (8) Poly-siloxane groups
• (9) Perfluorocarbon and partially fluorinated
  chains

14
??????????????
15
????????? Anionics
?????????
????????? Cationics
?????
???????? Double-Hydrophilic Group Surfactants
?????????? Zwitterionics
?????????? Polyoxyethylenated Nonionics
?????????
?? Other surfactants
???????? Polyalcohol Nonionics
Continue
16
IONIC SURFACTANTS ????????The surface-active
portion of the molecule is a ion
17

• 2 ANIONICS ?????????The surface-active portion
  of the molecule bears a negative charge for
  example
• RCOO- Na (soap).
• RC6H4SO3- Na (alkylbenzene sulfonate).
• Carboxylic Acid Salts
• Sulfonic Acid Salts
• Sulfuric Acid Ester Salts
• Phosphoric and Poly-phosphoric Acid Esters

18

• Carboxylic Acid Salts(???)
• CH3(CH2)nCOO-Me
• 1???Soaps Sodium and Potassium Salts of
• Straight-Chain Fatty Acid. Below 10carbons too
• soluble, above 20 carbons (straight chain), too
• insoluble or use in aqueous medium, but usable
  for
• nonaqueous systems (e.g., detergents in
  lubricating
• oils or dry-cleaning solvents).
• ?????(???)dodecanic (lauric acid)
• ?????(????)tetradecanoic (myristic acid)
• ?????(???)hexadecoic (palmitic acid )
• ?????(???)octadecanoic (stearic acid )

19

• Advantages Easily prepared and excellent
  physical properties for use in toilet soap bars.
• Disadvantages
• Form water-insoluble soaps with divalent and
  trivalent metallic ions,
• Insolubilized readily by electrolytes, such as
  NaC1,
• Unstable at pH below 7, yielding water-insoluble,
  free fatty acid.

20

• Major types and their uses
• (1) Sodium salts of tallow (??,animal fat)
  acids.(Tallow acids are oleic, 40-45 palmitic,
  25-30, stearic, l5-20.)Used in toilet soap bars
  and for de-gumming of silk, where alkaline
  solution is required. For industrial use in hard
  water, 1ime soap(??)dispersing agents (sulfonates
  and sulrates) are added to prevent precipitation
  of insoluble lime soaps.

21

• (2) Sodium and Potassium Salts of Coconut
  Oil(???) Fatty Acids
• (Coconut fatty acids are C12, 45-50, Cl4
  16-20, C168-10 oleic, 5-6, lt C12, 10-l5).
  Used as electrolyte-resistant soaps (seawater
  washing) and in liquid soaps, especially as the
  potassium soaps.
• (3)Sodium and Potassium Salts of Tall Oil
  Acids(????)
• (Tall oil, a by-product of paper manufacture
  is a mixture of fatty acids and rosin acids (???)
  from wood 50-70 fatty acid, mainly oleic and

22

• linoleic, 3050 rosin acids related to
  abietic acid, the main constituent of rosin.)
  Mainly "captive" use or in situ preparation for
  various industrial cleaning operations.
• Advantages
• Inexpensive. More water-soluble and hard-water
  resistant than tallow soaps. Lower viscosity
  solutions than tallow soaps at high
  concentrations, better wetting soaps of synthetic
  long-chain fatty acids are produced in Europe,
  but not in the United States at present.

23

• (4)??Amine Salts
• ?????Triethanolamine HN(C2 H4OH)3 sa1ts are
  used in nonaqueous so1vents and in situ
  preparation as an emulsifying agent (free fatty
  acid in oil phase, triethanolamine in aqueous
  phase).
• ???MorpholineHN(CH2CH2)2O , and other volatile
  amine(????) salts-used in polishes, where
  evaporation of the amine following hydrolysis of
  the salt leaves only water-resistant material in
  film.

24

• 2?Other Types
• (1) N-Lauroyl sarcoside, (N-???????)
• RCON(CH3)CH2COO-Na.
• Toothpaste(??) ingredient, since nontoxic,
  strongly foaming, and enzyme-inhibiting. Good
  detergency (like soap) and has advantage of being
  less sensitive to hard water and acids than the
  usual soap. Nonirritating to skin. N-Oleyl(??)
  sarcoside is a po1yester fiber lubricant(??).

25

• (2) Acylated Polypeptides????? (From partially
  hydro1yzed protein from scrap leather and other
  waste protein.)
• Used in hair preparations and shampoos, alkaline
  cleaning preparations, wax strippers. Good
  detergency and resistance to hard water.
• Advantages
• Soluble in concentrated aqueous solutions of
  alkaline salts.
• Nonirritating to skin

26

• reduces skin irritation produced by other
  surfactants (e.g., sodium 1auryl sulfate).
• Substantive to hair. Imparts soft "hand" to
  textiles.
• Disadvantages
• Precipitated by high concentrations of Ca2 or
  Mg2, acids (below pH 5).
• Lower foaming than laurylsulfates (??????).
• Requires foam booster (e.g., alkanolamides) when
  foaming is important.

27

• (3) Perfluorinated (???)Anionics
• Perfluorocarboxylic acids are much more
  completely ionized than fatty acids. They show
  good resistance to strong acids and bases,
  reducing and oxidizing agents, and heat (in
  excess of 316ºC in some cases).
• They are much more surface active than the
  corresponding carboxylic acids and can reduce the
  surface tension of water to much lower values
  than are obtainable with surfactants containing
  hydrocarbon groups.
• They are also surface active in organic solvents.
  Perfluoroalkyl sulfonates, too, have outstanding
  chemical and thermal stability.

28

• Uses. Emulsifiers for aqueous lattices of
  fluorinated monomers. Suppression of chromic
  acid mist and spray from chromium plating baths.
  "Light water" control of oil and gasoline fires.
  Formation of surfaces that are both hydrophobic
  and oleophobic on textiles, paper, and leather.
  Inhibition of evaporation of volatile organic
  solvents.
• Disadvantages. Much more expensive than other
  types of surfactants, resistant to biodegradation
  even when straight-chain.

29

• Sulfonic Acid Salts ???
• CH3(CH2)nC6H4SO3Me
• 1?Linear Alkyl Benzene Sulfonates (LAS????????)
• Advantages
• Comp1etely ionized, water-soluble, solubility is
  not arfectcd by low pH and hard water.
• Sodium salt is sufficiently soluble in the
  presence of e1ectrolyte (NaCl, NaSO4) for most
  uses.
• Resistant to hydrolysis in hot acid or a1kali.

30

• Disadvantages
• Sodium salt is not soluble in organic solvents,
  except alcohols.
• Linear dodecyl benzene sulfonate(????????) is
  resistant to biodegradation under anaerobic
  conditions, but is degradable under aerobic
  conditions.
• May cause skin irritation(??).

31

• 2? Higher Alkyl benzene sulfonates(??????)
  C13C15 homologs are more oil-soluble, and are
  useful as lubricating oil additives(??????).
• 3?Benzene-, Toluene-, Xylene-(???), and
  Cumene-sulfonates (???????)
• Are used as hydrotropes(?????), e.g., for
  increasing the solubility of LAS and other
  ingredients in aqueous formulations, for thinning
  soap gels and detergent slurries.

32

• 4?Ligninsulfonates (??????)
• These are a by-product of paper manufacture,
  prepared mainly as sodium and ca1cium salts, also
  as ammonium salts. They are used as dispersing
  agents for solids and as O/W emulsion
  stabilizers. They are sulfonated po1ymers of
  molecular weight 1000--20,000 of complex
  structure containing free phenolic, primary and
  secondary alcoho1ic, and carboxylate groupings.
  The sulfonate groups are at the ?- and
  ?-positions of C3 alky1 groups joining the
  phenolic structures. They reduce the viscosity of
  and stabilize aqueous slurries of dyestuffs,
  pesticides, and cement.

33

• Advantages They are among the most inexpensive
  surfactants and are availab1e in very large
  quantities. They produce very 1itt1e foam during
  use.
• Disadvantages Very dark color, soluble in water
  but insoluble in organic solvents. including
  alcohol. They produce no significant surface
  tension lowering. (Chemically modified
  derivatives, of lighter color, are available.)

34

• 5?Petroleum Sulfonates(?????)
• Products of the refining of selected
  petroleum fractions with concentrated sulfuric
  acid or oleum (????), in the production of white
  oils. Metal or ammonium salts of sulfonated
  complex cyc1oaliphatic and aromatic hydrocarbons.
• Uses
• Tertiary oil recovery (????)
• Sodium salts of lower molecular weight (435-450)
  are used as O/W emulsifying agents in soluble
  metal cutting oils(?????), frothing agents(???)
  in ore flotation(????), components of
  dry-cleaning soaps

35

• Sodium salts of higher molecular weight (465-500)
  are used as rust preventatives (???) and pigment
  dispersants(?????) in organic solvents.
• Ammonium salts are used as ash1ess rust
  inhibitors and soluble dispersants in fuel oils
  and gasoline.
• Mg, Ca, and Ba salts are used as siudge
  dispersants for fuel oils and as corrosion
  inhibitors for diesel lubricating oils(??????).
• Advantages Inexpensive.
• Disadvantages Dark in color. Contain
  unsulfonated hydrocarbon.

36

• 6?N-Acyl-n-Alkyltaurates(N-???????),
• RCON(R')CH2CH 2SO3-M
• The solubility, foaming, detergency, and
  dispersing powers of the N-methyl derivatives are
  similar to those of the corresponding fatty acid
  soaps in soft water
• These materials are effective both in hard and
  soft water, are not sensitive to 1ow pH, and are
  better wetting agents
• They show good stability to hydrolysis by acids
  and alkali, good skin compatibility, and good
  lime soap-dispersing power.

37

• Uses
• They show no decrease in foaming or lathering in
  combination with soap (in contrast with other
  anionics) in toilet bars and bubble baths .
• In alkaline bottle washing compounds and for
  seawater laundering, since their Ca and Mg salts
  are soluble.
• Impart soft feel ("hand") to fibers and fabrics
  (simi1ar to soaps and fatty alcohol sulfates, in
  contrast with nonionics and alkylarylsulfonates).
  
• Used as wetting and dispersing agents in wettable
  pesticide powders.

38

• 7?Paraffin Sulfonates, Secondary
  n-Alkanesulfonates (SAS??????)
• R1(R2)CH-SO3Me
• Produced by sulfoxidation(??) of n-paraffin
  hydrocarbons separated from refinery product
  streams (e.g., by molecu1ar sieves) with SO2 and
  O2 in the presence of ultraviolet 1ight.

39

• Uses. In detergents, similar to LAS. Unpurified
  paraffin su1fonates, containing about 50
  paraffin, arc used in fat liquoring of
  leather(????).
• Advantages
• Solubility in water is somewhat better,
• viscosity of aqueous solutions somewhat lower,
• skin compatabi1ity somewhat better,
• biodegradability at low temperature somewhat
  better than that of LAS of comparable chain
  1ength.

40

• 8??-Olefin Sulfonates (AOS ?-?????)
• Produced by reaction of SO3 with linear
  ?-o1efins. Product is a mixture of
  alkenesulfonates and hydroxyalkanesulfonates
  (mainly 3 - and 4-hydroxy).
• Advantages. Reported to be somewhat more
  biodegradable than LAS, less irritating to the
  skin. Show excellent foaming and detergency in
  hard water. High solubility in water allows
  products with high concentrations of actives.

41

• 9?Sulfosuccinate Esters ??????
• ROOCC H2CH (SO3-M)COOR
• Used
• Wetting agents for paints, printing inks,
  textiles, agricultural emulsions.
• The dioctyl(??) (2-ethylhexyl) (2-????) ester is
  soluble in both water and organic solvents,
  including hydrocarbons, and is therefore used in
  dry-cleaning solvents.
• Monoesters used in cosmetics.

42

• Advantages.
• Can be produced electrolyte-free, and is thus
  completely soluble in organic solvents and usable
  where electrolyte must be avoided.
• Amide monoesters are among least eye-irritating
  of anionic surfactants.
• Disadvantages.
• Hydrolyzed by hot alkaline and acidic so1utions.
• Dialkyl esters are irritating to skin (monoesters
  are not).

43

• 10?Alkylnaphthalenesulfonates
• (??????)
• Mainly butyl- and isopropyl-naphthalene-sulfonates
  , for use as wetting agents for powders
  (agricultura1 wettables, powdered pesticides).
• Also used as wetting agents in paint
  formulations(??).
• Advantages Available in non-hygroscopic(????)
  powder form for mixing into formulated powders.

44

• 11?Naphthalenesulfonic acid-formaldehyde
  condensates,
• (??????????)
• Uses. Similar to those for lignin(???) sulfonates
  (dispersing agents for solids in aqueous media,
  grinding aids for solids).
• Advantages over the usual lignin sulfonates are
  lighter color, even less foam.

45

• 12?Isethionates(?????????)
• RCOOCH2CH2SO3-M
• Used in cosmetic preparations, synthetic toilet
  soap bars, shampoos, bubble baths.
• Advantages.
• Excellent detergency and wetting power,
• Good lime soap dispersing power,
• Good foaming power.
• Less irritating to skin than AS (below).
• Disadvantages. Hydrolyzed by hot alkali.

46

• Sulfuric Acid Ester Salts
• for example lauryl sodium sulfate???????CH3(CH2)
  11OSO3Me
• 1?Sulfated Linear Primary Alcohols (AS)
• Sulfated coconut alcohol(???) from
  hydrogenation(??) of coconut oil
• Mainly C12 or sulfated tallow alcohols(???)
• Mainly oleyl(??), or sulfated synthetic alcohols
  from linear olefins to match these two types.

47

• Advantages
• Easily produced from alcohol and ClSO3H in
  neighborhood of room temperature in relatively
  simple equipment to yield very light-colored
  product.
• Excellent foaming properties, especially if some
  unsulfated alcohol is retained in product.
• Sulfated lauryl alcohol retains its excellent
  foaming properties even in hard water.
• Coconut alcohol derivative is suitable for food
  or pharmaceutical use.
• Disadvantages Hydrolyzed readily in hot acidic
  medium. May cause skin irritation.

48

• 2??????Sulfated Triglyceride Oils
• Produced by sulfation of hydroxy group and/or
  double boud in fatty acid portion of the
  triglyceride (Iodine values??40-140).
• Mainly castor oil ???used(12-hydroxyoleic acid),
  but also fish oils, tallow??, sperm oils??.
• Mainly used as textile wetting, cleaning, and
  finisfing agents. Also used as emulsifying agents
  in textile finishing in metal cutting oils, and
  so on.
• Advantage Cheap, easy to produce near room temp.
  by mixing oil and concentrated H2SO4.
• Disadvantage Readily hydrolyzed in hot acidic or
  hot alkaline solution.

49

• Phosphoric and Poly-phosphoric Acid Esters
• Mainly phosphated alcohols and phenols, some
  sodium alkyl phosphates.
• Advantages.
• The free acids have good solubility in both water
  and organic solvents, including some hydrocarbon
  solvents, and can be used in free acid form since
  acidity is comparable to that of phosphoric acid.
  
• Low foaming.
• Not hydrolyzed by hot alkali color unaffected.

50

• Disadvantages.
• Only moderate(??) surface activity as wetting,
  foaming, or washing agents.
• Somewhat more expensive than sulfonates.
• Na salts usually not soluble in hydrocarbon
  solvents.
• Uses.
• Emulsifying agents in agricultural emulsions
  (pesticides???, herbicides???), especial1y those
  blended with concentrated liquid fertilizer(????)
  solutions, where emulsion stabi1ity in presence
  of high electrolyte concentration is required
• Dry-cleaning detergents metal cleaning and
  processing. Hydrotropes (short-chain
  products).

51

• 3 CATIONICS?????????The surface-active portion
  bears a positive charge
• for examp1e, RNH3Cl- (salt of a 1ong-chain
  amine), RN(CH3)3Cl- (quaternary ammonium
  ch1oride).

52

• Advantages
• Compatible?? with nonionics and
  zwitterionics(????).
• Surface-active moiety has a positive charge, thus
  adsorbs strongly onto most solid surfaces (which
  arc usual1y negatively charged),
• Disadvantages
• Most types are not compatible wi1h anionics
  (amine oxides are an exception).
• Generally, more expensive than anionics or
  nonionics.
• Show poor detergency, on1y poor suspending power
  (????)for carbon.

53
Table 1-1 Some Uses of Cationics Resulting from
Their Adsorption onto Solid Substrates
54
Cationics in common use

• Long-Chain Amines and Their Salts
• Diamines and Polyamines and Their Salts
• Quaternary Ammonium Salts
• Amine Oxides (???)

55

• Long-Chain Amines and Their Salts
• Primary amines derived from animal and vegetable
  fatty acids and tall oil, synthetic C12C18
• 1?Primary amines CH3(CH2)11-17NH2 ,
• 2?Secondary R1(R2)NH,
• 3? Tertiary amines R1(R2)NR3.
• Adsorb strong1y onto most surfaces, which are
  usually negatively charged. Very solub1e and
  stable in strongly acidic solutions.
• Sensitive to pH changes--become uncharged and
  insoluble in water at pH above 7

56

• Uses.
• Cationic emu1sifying agents at pH below 7.
• Corrosion inhibitors(???) for metal surfaces, to
  protect them from water, salts, acids.
• Saturated, very long-chain amines best for this
  purpose, since these give close-packed
  hydrophobic surface films.
• Used in fuel and lubricating oils to prevent
  corrosion(??) of metal containers.

57

• Anticaking agents(????) for fertilizers,
• adhesion promotors(???) for painting damp
  surfaces(????).
• Ore flotation collectors(???????). forming
  non-wetting films on specific minerals, allowing
  them to be separated from other ores.
• Disadvantages.
• Poor leveling is characteristic of cationic wax
  or wax resin emulsions.

58

• Diamines and Polyamines and Their Salts
• for exampleCH3(CH2)nN(CH3)1-2HHCl
• Uses and properties similar to above.
• (RCONHCH2CH2)2NH are used as adhesion promotors
  for asphalt(??) coating of wet or damp road
  surfaces.
• Other uses. Ore flotation, to produce hydrophobic
  surface on ore or impurities
• Pigment coating, to make hydrophilic pigment
  lipophilic.

59

• Quaternary Ammonium Salts
• for exampleCH3(CH2)nN(CH3)3Cl-
• AdvantagesUnaffected by pH changes positive
  charge remains in acidic, neutral, and alkaline
  media.
• Disadvantages Since water solubility is retained
  at all pHs, they are more easily removed from
  surfaces onto which they may be adsorbed.

60

• 1?Tetraalky1ammonium salts of the type,
• R2N(CH3)2Cl-
  and
• 2?Imidazolinium salts(???) of structure
• (R from tallow or hydrogenated tallow) are used
  as textile softeners industrially and for home
  use in the rinse cycle of washing machines.
• They impart fluffy, soft "hand" to fabrics by
  adsorbing onto them with hydrophobic groups
  oriented away from fiber.

61

• 3?N-Alkyltri-methylammonium chlorides used as
• Emulsifying agents for acidic emulsions or where
  adsorption of emulsifying agent onto substrate is
  desirable (e.g., in insecticidal emulsions).
• Highly effective germicides(???) for industrial
  use. (Bis (long-chain alkyl) derivatives are less
  effective than monoalkyls oxyethylenation
  drastically reduces germicidal effect,
  chlorinated aromatic ring increases it.)

62

• 4?N - Benzyl- N - alkyl dimethylammonium halides
• 1227 or ????C12H25N(CH3)2CH2C6H4 Cl- or Br-
• are used as germicides(???), disinfectants(???),
  sanitizers (?????).

63

• They are compatible with alkaline inorganic salts
  and nonionics and are used together with them in
  detergent-sanitizers(?????) for public
  dishwashing.
• They are also used as hair conditioners (after
  shampoo rinses), since they adsorb onto hair,
  imparting softness and antistatic properties.
• The cetyl derivative is used in oral
  antiseptics(?????). Cetylpyridinium(??????)
  bromide is used in mouth washes.

64

• Amine Oxides (???) RN(CH3)2 O
• Usually, N-alkyldimethylamine oxides. These are
  usually classified as cationics, although they
  are actually zwitterionics.
• They are compatible with anionics, cationics, and
  nonionics, and other zwitterionics.
• Show excellent wetting in concentrated
  electrolyte solutions. The molecule adds a proton
  under the proper conditions, e.g., at low pH or
  in the presence of anionic surfactants, to form
  the cationic conjugate acid. The conjugate acid
  forms l 1 salts with anionics that are much more
  surface-active than either the anionic or the
  amine oxide.

65

• Used as foam stabilizer for anionics in
  detergents, liquid dishwashing compounds, and
  shampoos. Also increase the viscosity of the
  shampoo and manageability of hair.
  Cetyldimethylamine oxide(??????????) is used in
  electroplating baths(??). The stearyl derivative
  imparts a smooth "hand" to fabrics and hair.
• Advantage over alkanolamide form stabilizers.
  Effective at 1ower concentrations.

66

• 4 ZWITTERIONICS (AMPHIONICS)??????????Both
  positive and negative charges may be present in
  the surface-active portion.
• for example, RNH2CH2COO- (long-chain amino
  acid),
• RN
  (CH3)2CH2CH2SO3-(sulfobetaine).
• ?????????CH3(CH2)nNH2CH2CH2COO
• ?????????CH3(CH2)nN(CH3)2CH2COO

67

• Advantages. Compatible with al1 other types of
  surfactants. Less irritating to skin and eyes
  than other types. May be adsorbed onto negatively
  or positively charged surfaces without forming
  hydrophobic film.
• Disadvantages. Often insolub1e in most organic
  solvents, including ethanol.

68

• pH-Sensitive These are ampholytic materials,
  which may show the properties of anionics at high
  pHs and those of cationics at low pHs.
• IEP In the vicinity of their iso-e1ectric
  points they exist mainly as zwitterionics and
  show minimum solubility in water, and minimum
  foaming, wetting, and detergency.

69

• pH-Sensitive Zwitterionics
• weak acid weak base
• weak acid strong base
• strong acid weak base
• pH-Insensitive Zwitterionics
• strong acid strong base

70

• weak acid weak base
• 1??-N-Alkylaminopropionic Acid,
• RN (H2 )CH2CH2COO-
• IEP at pH 4. Very soluble in aqueous solutions
  of strong acids and alka1ies, even in the
  presence of electrolytes like NaCl.
• Solubility is low in most organic solvents,
  including ethanol and isopropyl alcohol.
• Adsorb from aqueous so1ution onto skin,
  textiles,fibers, and metals.

71

• On hair and textile, fibers they confer
  lubricity, softness, and antistatic properties
• On metals they act as corrosion inhibitors.
• They solubilize(??) many organic and inorganic
  compounds(e.g., quaternary ammonium salts,
  phenols, polyphosphates) in aqueous solutions.
• Effective emulsifying agents for long-chain
  a1cohols and slightly polar compounds, not good
  for paraffinic oils.

72

• Emulsions can be converted from anionic to
  cationic by pH adjustment.
• Emulsions more easily prepared at alkaline than
  at acidic pHs.
• N-Dodecyl derivative is an excellent wetting
  agent and foam producer at alkaline pHs, less of
  a foamer at acid pHs.
• Uses. Bactericides, corrosion inhibitors, pigment
  dispersion aids, cosmetics, alkaline cleaners
  with high alkali and electrolyte content.

73

• 2?N-Alkyl-?-iminodipropionic Acids(?????????),
• IEP, pH l.7-3.5.
• More soluble in water than corresponding
  mono-propionic acid derivatives.
• Show very low order of skin and eye irritation.
• May be removed from substrates onto which they
  have adsorbed at pHs below their iso-electric
  points by raising the pH.
• Uses. Fabric softeners.

74

• 3?Imidazoline carboxlates,
• R from RCOOH of commercially
• available fatty acids. When R' is H
• they are ampholytic(??).
• Compatib1e with anionics, cationics, and
  nonionics, soluble in water in the presence of
  high concentrations of electrolytes, acids, and
  alkalies.
• When R' contains a second carboxylic acid group,
  products show a very low order of skin and eye
  irritation.
• Uses. Cosmetic and toilet preparations, fabric
  softener (which can be removed from substrate by
  increase in pH to the alkaline side).

75

• weak acid strong base
• 1?N-Anylbetaines, RN(CH3)2CH2COO (?????)
• These materials are zwitterionic at pHs at and
  above their iso-electric points (neutral and
  alkaline pHs) and cationic below their
  iso-electric points (acid pHs). They show no
  anionic properties.
• Compatible with al1 classes of surfactants at
  all pHs except that at low pHs they yield
  precipitates with anionics.
• Acid and neutral aqueous so1utions are compatible
  with alkaline earth(??) and other metallic ions
  (A13, Cr3, Cu2,Ni2, Zn2 ).

76

• They show minimum skin irritation at pH 7.
• Show constant adsorption onto negatively charged
  surfaces (as cationics), irrespective of pH.
• Slightly better wetting and foaming properties at
  acidic than at alkaline pHs.
• Hard water has no effect on foaming properties in
  aqueous solution.
• Emulsification properties are similar to those of
  ?-N-alkylaminopropionic acids (not good for
  paraffinic oils). lttUses. Similar to those of
  g-N-alkylaminopropionic acids.

77

• strong acid weak base
• RN (H2 )CH2CH2SO3-

78

• pH-Insensitive Zwitterionics
• strong acid strong base
• These rnaterials are zwitterionics at all pHs (at
  no pH do they actmere1y like anionics or
  cationics).
• Sulfobetaines(?????), Sultaines,
  RN(CH3)2(CH2)2SO3
• Adsorb onto charged surfaces at all pHs without
  forming hydrophobic films. Good lime soap(??)
  dispersants.
• Uses. Similar to other zwitterionics. Lime soap
  dispersants in soap-detergent formulations.

79

• Phosphated Zwitterionics lecithin(???)
• Double Chains

80

• 5 NONlONlCS(?????????)The surface-active
  portion bears no apparent ionic charge,
• for example,
• RCOOCH2CHOHCH2OH (monoglyceride of long-chain
  fatty acid), (??????????)
• RC6H4(OC2H4OH)xOH (polyoxyethylenated
  alkylphenol), (?????)

81

• Advantages.
• Compatib1e with all other types of surfactants.
• Can be made resistant to hard water, polyvalent
  metallic cations, electrolyte at high
  concentration
• Soluble in water and organic solvents, including
  hydrocarbons. Polyoxyethylenated nonionics are
  generally excellent dispersing agents for carbon.
• Disadvantages.
• Products are liquids or pastes, rarely nontacky
  solids.

82

• Poor foamers (may be advantage sometimes)
• No electrical effects (e.g., no strong adsorption
  onto charged surfaces).
• Ethylene oxide derivatives show inverse
  temperature effect on solubility in water, may
  become insoluble in water on heating.
• Commercial material is a mixture of products with
  a wide distribution of polyoxyethy1ene chain
  lengths.
• Polyoxyethylene chains with terminal hydroxyl
  (???)show yellowing (due to oxidation) in strong
  alkali that can prevented by etherifying
  ("capping") the hydroxyl

83

• 1?Polyoxyethylenated Alkylphenols,
• Alkylphenol Ethoxylates"(APE)
• Mainly polyoxyethylenated p-nonylphenol(???),
  p-octylphenol(???), or p-dodecylphenol(?????)(some
  times, dinonylphenol), derived from disobutylene,
  propylene trimer, or propylene tetramer.
• OP-n series C8-12H17-25-C6H4-O-EOn
• OP-10 n10

84

• Advantages.
• Length of alkyl group on phenol or POE chain can
  be varied to give range of products varying in
  solubility (1-5 mol of ethylene oxide).
• POE linkages are stable to hot dilute acid,
  alkali, and oxidizing agents results from
  hydratable multip1e ether linkages.
• There is never any free alkylphenol in APE, since
  phenolic OH is more reactive than alcoho1 OH.
• Disadvantages More resistant to biodegradation
  than other non-ionic types.

85

• Uses. Mainly industrial.
• Water-.insoluble types used for W/O emulsifying
  agents, foam contro1 agents, coso1vents
• Water-soluble types for O/W emulsifying agents
  for paints, agricultural, industrial and cosmetic
  emulsions.
• Materials with high ethylene oxide (EO) content
  (gt l5 mol of EO) are used as detergents and
  emulsifiers in strong electrolyte systems and as
  foam entrainment agents in concrete.
• Also used in liquid detergents and as dyeing
  retarders(???) for cellulose (surfactant forms
  complex with dye molecules).
• Excellent dispersing agents for carbon.

86

• 2?Polyoxyethylenated Stralght-Chain Alcohols,
  Alcohol "Ethoxylates" (AE)
• JFc C7-9H15-19-O-EO5-6
• ???O(20) C12-18H25-37-O-EO20
• Mainly mixed coconut oil-derived, tallow-derived,
  and synthetic straight-chain alcohols are used as
  the hydrophobes, both primary and random
  secondary
• Uses for industrial purposes similar to those of
  APE. In low- and controlled- foam laundry
  detergents.
• Advantages.
• More easily biodegraded than alkylphenol
  ethoxylates,

87

• More resistant to hydrolysis in hot alkaline
  solutions than POE fatty acids,
• more water-soluble and better wetting powers than
  corresponding fatty acid ethoxylates.
• Somewhat better than the corresponding APE for
  emulsification.
• More water-soluble than LAS, for use in high
  active, heavy-duty liquid detergents free of
  phosphates.
• More effective detergency than LAS under cool
  washing conditions and on synthetic fabrics.
• Disadvantages. Contain appreciable amounts of
  non-oxyethylenated hydrophobe.

88

• 3?Polyoxyethylenated Polyoxypropylene Glycols
• Block copolymers of ethylene oxide and propylene
  oxide.
• Materials with low ethylene oxide content have
  very little foam
• Materials of high molecular weight with low EO
  content are wetting agents.
• Materials with high EO content are dispersing
  agents. Products range in molecular weight from
  1,000 to 30,000.

89

• Uses.
• High-molecular-weight materials with high EO
  content are used as dispersants for pigmcnts in
  latex paints or for scale removal in boilers
• low-molecular-weight materials with low EO
  content are usedas foam control agents in laundry
  detergents and in rinsing aids for dish washing.
  Petroleum demulsifiers(???).

90

• Advantages.
• Both hydrophobic group CH2CH2(CH3)Ox and
  hydrophilic group CH2CH2Oy can be varied at
  will to "tailor make" product with specific
  properties.
• Products with high-molecular-weight hydrophobes
  and high EO contents are nontacky solids
  (?????)(in contrast to other POE nonionics).
• Better wetting agents than ester-type nonionics.

91

• 4?Polyoxyethylenated Mercaptans(??)
• RSO CH2CH2OyH
• Unstable to oxidizing agents, such as
  chlorine(?), hypochlorites(????),
  peroxides(????), and strong acids. (This may be
  an advantage when inactivation of surfactant
  after use is desired.)
• Stab1e in hot, strong alkali.
• Good lime soap(??)dispersants.
• Uses. Textile detergents (cleaning and scouring
  of wool), metal cleaning, shampoos.

92

• Advantages.
• POE mercaptans (??) are more effective as
  detergent sanitizers(???) rather than with other
  POE nonionics.
• Disadvantages. Have slight, unpleasant odor that
  is difficult to mask.

93

• 5?Long-Chain Carboxylic Acid Esters
• Advantages.
• In some cases, very easi1y made in simple
  equipment.
• Outstanding emulsifying properties, compared to
  other nonionic types.
• Disadvantages.
• Readily hydrolyzed by hot acids or hot alkalies.
• Lower foam than other nonionic types (may be
  advantage for some uses).

94

• 6?Polyoxyethylenated Silicones
• These are the reaction products of a reactive
  silicone intermediate, with a capped allyl
  polyalkylene oxide, such as CH2CH-CH2-(OC2H4)-OR1
  , to yield
• The resulting structure is a "comb" polymer,
  with pendant capped hydrophi1ic groups. In
  aqueous solution, the hydrophilic groups may form
  a sheath around the hydrophobic si1icone backbone
  to minimize its contact with the water.

95

• 1?Glyceryl and Polyglyceryl Esters of Natural
  Fatty acid(?????????),
• Advantages.
• Easily made by g1ycerolysis of triglycerides or,
  somewhat more expensively, by esterification(??)
  of fatty acids with glycerol in simple equipment.
  
• Edible(???), hence sable in food and
  pharmaceutical products.
• May be liquid, soft plastic, or hard wax,
  depending on fatty acid composition.
• Can be modified by reaction with acetic,
  lactic(??), or tartaric acids(???).

96

• Disadvantages.
• Mixture of mono- and diglycerides (glycerides of
  l90 monoester content must be made by
  distillation of usual reaction product).
  Mono-glyceride is a better emulsifier than
  di-glyceride.
• Uses.
• Cosmetic emulsifiers, food emulsifiers for bread,
  ice cream, margarine(????), synthetic
  cream(????), and other dairy products(????).

97

• 2?Propylene Glycol(???), and Sorbitol(???) Esters
  
• Propylene glycol esters are more lipophilic than
  the corresponding glycerol(??) esters
• sorbitol esters are more hydrophilic (unless
  dehydrated in course of manufacture).

Span series
98

• Polyoxyethylene Glycol Esters and
  Polyoxyethylenated Fatty Acids(Including Tall
  Oil)
• Prepared either by esterification of
  polyoxyethylene glycol with fatty acid or by
  addition of ethylene oxide to fatty acid.
• Tall oil derivatives have lower foaming
  properties than corresponding fatty acid
  derivatives.

99

• Advantage
• over glyceryl esters in that length of
  hydrophilic group, and hence so1ubility and
  hydrophilic-lipophilic balance of product, can be
  varied as desired.
• Generally better emulsifying agents than AE or
  APE.

100

• Disadvantages. Generally poor wetting properties,
  hydrolyzed by hot alkaline solutions.
• Uses.
• Emulsification of all sorts, especially in
  cosmetics and for textile use, except where hot
  alkaline solutions are encountered.
• Textile antistatic.

101

• Minimum surface tensions for products of this
  type in aqueous so1ution fall in the 20- to
  25-dyn/cm range at 25'C.
• They are excellent wetting agents at
  concentrations of a few hundredths of a percent
  for cotton and
• show good lubricating properties of textile
  fibers.

102

• They are also excellent wetting agents for
  polyester and polyethylene.
• They are low to moderate foamers in aqueous
  solution.
• They can also be used to lower the surface
  tension of nonaqueous solvents such as
  po1yalkylene glycols.

103

• Alkylpolyglycosides (?????)
• These are long-chain acetals of
  polysaccharides. Commercial products currently
  available have relatively short alkyl chains
  (averaging 10 and l2.5 carbon atoms).

104

• They show wetting, foaming, detergency, and
  biodegradation properties similar to those of
  corresponding alcohol ethoxylates, but higher
  solubi1ity in water and in solutions of
  electrolytes.
• They do not appear to show the inverse solubility
  (cloud point) characteristic of ethoxy1ated
  nonionics and consequently do not show any abrupt
  change in properties with temperature increase.

105

• They are also soluble and stable in sodium
  hydroxide solutions, in contrast to AE.
• Although effective fatty soil removers, they show
  very low skin irritation and are recommended for
  hand liquid dishwashing and hard surface
  cleaners.

106
6. ????????Surfactants of Double-hydrophilic
Group

• Nonionic Nonionic Surfactants
• Anionic Nonionic Surfactants
• Cationic Nonionic Surfactants

107

• Polyoxyethylenation of sorbitol (and
  anhydrosorbitol produced during manufacture)
  gives wide range of solubilities and
  hydrophilic-lipophilic balances to products.
• Advantages. Edible???, thus useful for food and
  drug use (e.g., soluble vitamins)
• Uses. Food and pharmaceutical emu1sifiers.

Tween series
108

• 1?Sulfated Polyoxyethylenated Straight-Chain
  Alcohols (AES), R(OC2H4)xSO4-M (x 3, usually)
  
• Advantages over AS. More water-soluble, more
  electrolyte resistant, much better lime soap
  dispersing agents, foam more resistant to water
  hardness and protein soil. NH. salt is less
  irritating to skin and eyes, produces higher
  viscosity solutions (advantages in shampoos).
• Uses. In light-duty liquid detergents to
  improve foaming characteristics together with
  nonionic in heavy-duty liquids free of
  phosphates, in shampoos.

109

• 2?Polyoxyethylenated Phosphoric and
  Poly-phosphoric Acid Esters

The polyoxyethylenated (POE) materials are
available in free acid form or as Na or amine
salts. Products are mixtures of mono-basic and
dibasic phosphates and show good resistance to
hard water and concentrated electrolyte.
110

• 1?Polyoxyethylenated (POE) Long-Chain Amines
• RN(CH2CH2O)xH2
• Combine increased water solubility imparted
  by POE chains with cationic characteristics of
  the amino group. As the oxyethylene (OE) content
  increases, cationic properties decrease and
  materials become more like nonionics in nature
  (e.g., solubility in water does not change much
  with pH change, incompatibility with anionics
  diminishes). If OE content is high enough,
  materia1s do not require acidic solution for
  water solubility.

111

• Uses.
• In production of xanthate(???) rayon to improve
  tensile strength or regenerated cellulose
  filaments and to keep spinnerets free of
  incrustations.
• Emulsifying agents for herbicides, insecticides,
  polishes, and wax emu1sions, which "break" on
  contact with the substrate and deposit the oil
  phase on it.

112

• Advantages.
• Salts with inorganic or low-molecular-weight
  organic acids are water-soluble,
• those with high-molecular-weight organic acids
  are oil-soluble, even when the free POE amines
  are oil-insoluble.
• Show inverse solubility in water on heating, like
  other polyoxyethylene derivatives.

113

• 2?Quatemized Polyoxyethylenated (POE) Long-Chain
  Amines
• RN(CH3)(C2H4O)xH2C1-is used as textile
  antistatic agent (ionic charge dissipates static
  charge polyethylene group adsorbs water, which
  also dissipates charge).
• Also used as dyeing leveler (retarder??) by
  competing transiently for dye sites on fabrics
  during the dyeing process, thereby decreasing the
  rate of dyeing at its most active sites-where it
  is most rapid1y adsorbed to that of the 1ess
  active sites. This causes more uniform dyeing.
• Used as corrosion inhibitors for metallic
  surfaces.

114

• 3?(RCONHCH2CH2)2N (CH3)(CH2CH2O)xHCH3SO4 (RCO
  from tallow) is used as fabric softener in rinse
  cycle of laundry washing.
• Promotes adhesion in asphalt (by adsorption to
  form hydrophobic, oleophilic surface film on
  substrate).
• Dispersing agent for clay in greases, emulsifying
  agent for polar compounds (e.g., fatty acids and
  amines) in O/W emulsions. Trifluoroacetate salts
  are used to produce foam that reduces chromic
  acid spray and mist in chromium plating.
• RCONH(CH2)3N(CH3)2CH2CH2OHNO3- is used as a
  surface or interna1 antistatic for plastics.

115
7 Some special Surfactants

• Polymeric Surfactants
• 2. Bio-Surfactants

116

• 1. Polymeric Surfactants
• Advantages Show excellent dispersibility,
  flocculabbility , solubilization ,
  emulsification, foaming stabilization ,
  thickening action (????),and very low irritation
  and toxicity.
• Disadvantages Somewhat lower detergency ,
  foaming ability, penetrability(???). They can not
  be used to lower the surface tension of water
  solutions.

117
?-???????????????????
118

• Water-Soluble Polymer
• Anionic polymeric surfactants
• Carboxylic Acid Salts

119

• Sulfuric Acid Ester Salts

120

• Sulfonic Acid Salts

121

• Cationic polymeric surfactants
• Amines and Their Salts

122

• Quaternary Ammonium Salts

123

• Nonionic polymeric surfactants

124

• Zwitterionic Polymeric Surfactants

125
???????????
126

• Polysoaps (Amphiphilic Polymers)

127
(No Transcript)
128
Single Molecule Micelle
129

• Molecular Structure of Polymeric Surfactants
• Random copolymers
• Block copolymers
• Graft copolymers

130

• 2. Bio-Surfactants
• (?) What is the Bio-Surfactants?
• A series of surface active metabolites
  (????????????????????)which are produced by
  microorganism zymolysis, besides the surfactants
  (??????????,????????) extracted from
  organism. ?
• Classify by Surface activity of the
  Bio-Surfactants
• Bio-SurfactantsLower molecular weight can be
  use to lower the surface or interface tension and
  adsorption, wetting, emulsification,
  solubilization, and dispersing.

131
(No Transcript)
132

• Bio-EmulsifiersBio-Macromolecule
• It can not be use to lower the surface or
  interface tension markedly
• A better emulsification.
• Coefficient of diffusion 5.2?10-8cm2/s
• reduced viscosity (????) 750cm3/g
• MW 9.8 ?105 .

133

• Advantage
• Safenessvery good bio-degradation and very low
  toxicity corresponding chemical synthetic
  surfactants
• Economics
• Culture medium(???)price
• Production processseparation and purification
• yieldhigh or low?

134

• Solubility
• water and
• polar organic solvent
• methanol, ethanol , acetone
• Stability
• e.g.glulcolipid
• 20-90ºC
• pH 1.7-11.4
• Higher concentration of electrolyte

135

• Disadvantage Very expensive
• Molecular structure
• Mostly of bio-surfactants are nonionics and
  anionics, a few of them are zwitterionics, no
  cationics.
• Hydrophobic R-CO-
• Hydrophilic
• neutral R-COO- and R-OH
• fatty acid or amino acid R-COOH
• phospholipid (??) ROPO2O
• Glulcolipid(??) glycosyl

136

• Uses
• Agriculture emulsification, wetting,
• solubilization,
  disperse
• Architecture(??) wetting, foaming
• Foodstuff industry petroleum all field
• Leather industry emulsification, wetting,
• soil removal
• Paints pigments emulsification, wetting,
• antistatic
• Textile industry - emulsification, wetting,
• soil removal,antistatic, solubilization,
  disperse.

137

• (? ) Classification of Bio-Surfactants
• Glycolipid(??) one of the most variety
• Rhamnolipid(????) Products of four kinds
• Rhamnolipid R1 by Pseudomonas( ????, ??), 37ºC,
  glucose(???), 4-8days.
• Advantage better emulsification than Tween
  series, somewhat micro-organism resistance,
  antivirus.

138

• Rhamnolipid R2 by Pseudomonos aeruginosa KY4025
  in 10 n-paraffine, at30ºC, 55hr.
• R1 H R2 ?-????
• two fatty acid and one rhamnose
  group
• Rhamnolipid R3 and R4 by Pseudomonos sp.DSM
  2874, at 30ºC, NaCl aq.
• one fatty acid
• R3 R1 L-?-?????? R2 H
• R4 R1 H R2 H
• good emulsifiers then
• Tween

139

• other Rhamnolipid
• containing free carboxyl

140

• Fucose glulcolipid (????) nonionics
• For example cord factor(???? or
  ???-6,6-O-?????)by Rhodococeus
  erythroropolis(??)
• as follows mn27-31, ????????

mycolic acid (???)C60-90 nocardomycolic
acid (??????)
C40-50 corynomycolic acid (?????)
C25-40 Other Mono-ester(??)
CMC in water is 4ppm
141

• Sophorose glycolipid(???)
• Simple surfactants of low MW by Torulopsis
  sp.(???)
• Two kinds of glycolipids as follow

Acid type
Intra-ester or lactone type
142

• Cellobiose glulcolipid (?????) by Ustilago zeae
  PRL 119(???????)

R H or OH
143

• Amino acid lipoid(??????)
• Ornithine lipoid(????) Pseudomonas rubescens
  (????) zwitterionics

Containing free amido and carboxyl as fig.
144

• Surfactin(??) by Bacillus subtilis(??)
• L-Glu L???OOCCH2CH2CH(NH3)COO
• L-Leu - ???(CH3)2CHCH2 CH(NH3)COO
• L-Val - L???(CH3)2CHCH(NH3)COO.

145
Classification of Biosurfactants
Bioemulsifier in Industry
B1-4
146
(No Transcript)
147
(No Transcript)
148
(No Transcript)
149
Applications of Biosurfactants Bioemulsifier in
industry
150
(No Transcript)
151
Procedure of Biosurfactants Bioemulsifier
152
(No Transcript)
153
(No Transcript)
154
7 The Solubility of Surfactants

• 1. The Krafft Temperature
• ?????? TK(lauryl sodium sulfate and H2O)
• ?????????????????????????
• (1) Two Lines
• The solubility curve
• T lt TK and T gt TK two regions
• (b) The CMC curve

155

• (2) The four areas
• Dilute solution unsadturated solution
• Sadturated solution crystalline hydrate
• Micelle solution
• Micelle solution crystalline hydrate

156

• (3) Affect of Concentration
• T lt TK
• dissolution ? saturated
• supersaturated ?
• crystalline hydrate ?
• adsorption on surface is not sufficiency
• (b) T gt TK
• dissolution ? adsorbed
• adsorption saturated
• micelle formation? adsorption on surface is
  sufficiency

157

• (4) Affect of Temperature
• From a supersaturated solution of surfactants
• T lt TK, T?
• solubility? , crystalline
• hydrate ?, adsorption?,
• surface tension of solution?
• (b) T TK, T?
• solution ? micelle solution ,
• crystalline hydrate ? disappear,
• adsorption ? saturation ?,
• surface tension of solution ? constant ?

158

• (c) T gt TK, T? ,
• solution? saturation ,
• crystalline hydrate ? dissolve,
• adsorption ? saturation,
• surface tension of solution ? constant

159

• (5) Factors of influence
• (a) Hydrophobic groups
• hydrophobicity ?, TK?
• degree of un-saturation ?, TK?
• degree of branching ?, TK?.
• (b) Additives
• Electrolyte , I(1/2)?CiZi2 ?, radius of ionic
  atmosphere ?, hydrophilicity ? , TK?
• Regulator of water structure(??????)
• Promoters ? fructose,xyloseTK ?
• Breakers ? urea,lower alcohol TK ?
• (6) Mensuration of TK 1 concentration

160
The Krafft Point of some Compounds
161
The Krafft Point of some Compounds
162
(No Transcript)
163
Relation curve between solubility of ionic
surfactants and temperature
164

• 2?Cloud point of Polyoxyethylene(PEO) nonionics
• Cloud point(TP) - T ? TP, phase separation
• Cloud point and hydrogen bond
• T?
• hydrogen bond ?
• hydrophility ?
• phase separation

165
(b) Phase diagram Low Critical Solution
Temperature(b)
(LCST)

• ???
• UCST
• (b)???
• LCST
• ??
• UCST and
• UCST

T lt Tp one phase T gt Tp two phase
166
(No Transcript)
167

• (2) Factors of influence
• Hydrophilic groups n ? hydrophilicity ?, TP?
• Hydrophobic groups ?
• R ? hydrophobicity ?, TP ?
• degree of un-saturation ?, TP?
• degree of branching ?, TP?.

168

• (c) Additives
• Electrolyte , I(1/2)?CiZi2 ?, break of hydrogen
  bond ?, hydrophilicity ? , TP?
• HCl TP ?
• Regulator of water structure(??????)
• Promoters ? fructose,xyloseTP?
• Breakers ? urea,lower alcohol TP ?
• (3) Mensuration of TP 1 concentration

169
Relation curve between TP and EO
170
Relation curve between TP and concentration
of surfactants
171
Relation curve between TP and ionic strength
172
The Cloud Point of some Compounds
173
The Cloud Point of some Compounds
174

• END