Emulsifier

Department of Food Science and Technology IPB/DIN/2011

Emulsions
Liquid/liquid systems of 2 immiscible substances Substances of particle size = 10-100 microns

oil oil oil

oil oil

H2O H2O H2O

H2O H2O

water Oil in water (O/W)

oil Water in oil (W/O)

Department of Food Science and Technology IPB/DIN/2011

Example :
W/O butter margarine O/W mayonnaise salad dressing milk cream

Department of Food Science and Technology IPB/DIN/2011

Stability of Emulsion depends on :

Droplet size /energy output Quality of the interfacial films Viscosity of outer phase Ratio of the two phases Specific density of the two phases

Department of Food Science and Technology IPB/NAN/2011

Margarine
Oil

EMULSIFIER
Emulsifier
Hydrophobic group

water

Hydrophilic group

Mayonnaise

Oil

Water

Allow water and oils to remain mixed together in an emulsion

Department of Food Science and Technology IPB/NAN/2011

DESTABILIZATION OF THE DISPERSION

Oil Oil Oil Oil Oil Oil Oil Oil Oil Oil Oil Oil Oil Oil Oil Oil

Water

Oil
Oil

Oil
Oil Oil

Oil Oil
Oil Oil

Oil

Aggregation

Water

Oil

Water

Oil separation from water

Department of Food Science and Technology IPB/NAN/2011

FUNCTIONS
1. To assist stabilization and formation of emulsion the reduction of surface tension at the oil-water interface (margarine & mayonnaise) 2. Alteration of the functional properties of other food components (bakery products: crumb softener, dough conditioner) 3. To modify the crystallization of fat (the reduction of bloom in certain candy products) 4. Change foods texture Form the complex compounds with carbohydrate (starches) and protein improve foods texture
Department of Food Science and Technology IPB/DIN/2011

SOME DESIRABLE CHARACTERISTICS OF FOOD EMULSIFIERS

1. Ability to reduce interfacial tension below 10 dynes/cm 2. Ability to be rapidly absorbed at the interface 3. Ability to function effectively at low concentrations 4. Resistance to chemical change 5. Lack of odor, color, and toxicity 6. Economical

Department of Food Science and Technology IPB/NAN/2011

Emulsifier selection :
Final product characteristics Emulsion preparation methodology The amount of emulsifier added The chemical and physical characteristics of each phase The presence of other functional components in the emulsion Approval by government (legal emulsifier) Processing parameters Synergistic effect of other ingredients
Department of Food Science and Technology IPB/DIN/2011

Most important functions of Emulsifiers

Stabilizations of emulsifiers Starch complexing Protein interaction Fat crystallization Viscosity control Foaming and aeration Lubrication - baked goods - bread - margarine, shortening - chocolate - desserts - extruded products
Department of Food Science and Technology IPB/NAN/2011

Composition of Food Emulsifiers

OH-Component Glycerol Glycerol Glycerol Glycerol Glycerol Glycerol Glycerol Glycerol Glycerol Sucrose Sorbitol Sorbitol Polyglycerol Propylene Lactic Acid Tartaric Acid Acid-Component Phosphoric acid Phosphoric acid Acetic acid Lactic acid Citric acid Acetic-/tartaric acid Succinic acid Others Amino component Ammonium Ethylene oxide Ethylene oxide Sodium, calcium Emulsifier Lecithin's Ammonium phosphatides Monoglycerides Ethoxylated monoglyceride ACETEM LACTEM CITREM DATEM Succinic ester of monoglyc. Sucrose ester Sorbitan ester Polysorbates Polyglycerol ester, PFPR Prophyleneglycerol ester SSl, CSL Stearyl tartrate

Department of Food Science and Technology IPB/NAN/2011

HLB concept
Hydrophillic-Lipophillic Balance
A concept for choosing emulsifiers Based upon the relative percentage of hydrophilic to lipophilic groups within the emulsifier molecule The value of HLB range from 1-20
Lower HLB : a more lipophilic emulsifier Higher HLB : a more hydrophilic emulsifier
Department of Food Science and Technology IPB/DIN/2011

Function of Emulsifiers in Relation to the HLB-Value

HLB 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18
Department of Food Science and Technology IPB/NAN/2011

Application Antifoaming agents W/Oemulsifies

Wetting agents

O/Wemulsifiers

solubilizer

HLB VALUES OF SOME FOOD EMULSIFIERS

Acetylated monoglycerides (stearate) Sorbitan monooleate Propylene glycol monolaurate Sorbitan monostearate Calcium stearoxyl-2-lactylate Glycerol monolaurate Sorbitan monopalmitate Soy lecithin Diacetylated tartaric acid esters of monoglycerides Sodium Stearoyl lactylate Sorbitan monolaurate ) Polyoxyethylene (20) sorbitan tristearate Polyoxyethylene (20) sorbitan trioleate Polyoxyethylene (20) sorbitan monostearate Sucrose monolaurate Polyoxyethylene (20) sorbitan monooleate Polyoxyethylene (20) sorbitan monopalmitate 3.8 4.3 4.5 4.7 5.1 5.2 6.7 8.0 8.0 8.3 8.6 10.5 11.0 14.9 15.0 15.0 15.6

Department of Food Science and Technology IPB/DIN/2011

Limitation of HLB system

HLB system does not work well for ionic emulsifiers the charge varies with pH Commercial preparation usually contain two or more emulsifier HLB system based upon the molecular structure of emulsifier does not take into account the combined oil/aqueous phase/emulsifier system

Department of Food Science and Technology IPB/DIN/2011

Limitation of HLB system

The inability to take into account : i. The effect of temperature ii. The presence of additives iii.The concentration of emulsifying agents

Department of Food Science and Technology IPB/DIN/2011

Lecithin
Phosphatidylcholine and mixtures of phospholipids Source : soybeans, corn, sunflower, cottonseed, rapeseed, eggs HLB 8.0 Partially soluble in water Regulation/safety : safe as food emulsifier FDA GRAS (Generally Recognize as Safe) The EU Food additive (E322) Codex INS No. 322
Department of Food Science and Technology IPB/DIN/2011

The primary phospholipids reported in commercial lecithin, where R1 and R2 are fatty acids
Department of Food Science and Technology IPB/DIN/2011

Mono- & diglycerides of fatty acids

Most commonly used as food emulsifier Synonyms :
Glyceryl monostearate, glyceryl monopalmitate, glyceryl monooleate, etc Monostearin, monopalmitin, monoolein, etc. GMS (for glyceryl monostearate)

Formula weight
Glyceryl monostearate: 358.6 Glyceryl distearate: 625.0
Two major components of commercial products

White or cream colored hard fats of waxy appearance, plastic products or viscous liquids
Department of Food Science and Technology IPB/DIN/2011

Mono- & diglycerides of fatty acids

Insoluble in water soluble in ethanol, chloroform and benzene HLB values range 1-10 Produced by transesterification of glycerol and triacylglycerides Safety FDA GRAS (Generally Recognize as Safe) The EU Food additive (E471) Codex INS No. 471 Used in bakery products, frozen desserts, icings, toppings, and peanut butter
Department of Food Science and Technology IPB/DIN/2011

Monoglyceride

Diglyceride

Di-glycerides ( di-stearate)
O

Mono- Glycerides (mono-stearate)

O CH2 HO HO CH CH2 O C (CH 2 )16 CH3 HO

CH2 CH CH2

C (CH CH3 2 )16 O O C (CH CH3 2 )16

Hydrophobic

Hydrophilic

Hydrophobic

Hydrophilic

Department of Food Science and Technology IPB/DIN/2011

Acid ester of mono- and diglycerides

Department of Food Science and Technology IPB/DIN/2011

ACETEM (E472a)
Synonyms :
Acetic acid esters of mono- and diglycerides Acetoglycerides Acetylated mono- and diglycerides Acetic- and fatty acid esters of glycerol Mono- and diglycerides of fatty acids esterified with acetic acid

Solubility
Insoluble in strongly polar solvent (water, glycerol) Dispersible to soluble in edible oil/fats and some alcohol (ethanol, iso-propanol)
Department of Food Science and Technology IPB/DIN/2011

LACTEM (E472b)
Synonyms :
Lactic acid esters of mono- and diglycerides Lactoglycerides Lactic acid and fatty acid esters of glycerol Mono- and diglycerides of fatty acids esterified with lactic acid Glycerol-lacto esters of fatty acids Lactated mono- and diglycerides

Solubility
Insoluble in hot water and 1,2-propylen-glycol Soluble in some hot alcohol (ethanol, iso-propanol or xylol) and fats (soybean oil/lard)
Department of Food Science and Technology IPB/DIN/2011

CITREM (E472c)
Synonyms :
Citric acid esters of mono- and diglycerides of edible fatty acids Mono- and diglycerides of fatty acids esterified with citric acid Monoglycerol citric acid esters Monoglycerol citrates Citric acid monoglycerides Citric acid monoglycerol esters Citric acids ester of glycerides Citric acid-fatty acid-glycerides Citric- and fatty acid esters of glycerol Citroglycerides
Department of Food Science and Technology IPB/DIN/2011

DATEM (E472d)
Synonyms :
Diacetyltartaric acid esters of mono- and diglycerides Diacetyltartaric and fatty acids ester of glycerol Mono- and diglycerides of fatty acids esterified with diacetyltartaric acid

Solubility :
Dispersible in hot/cold water Offer certain solubility in warm fats, oils, methanol/ethanol, acetone

ADI 0-50 mg/kg bw (JECFA) Interact with starch and flour protein in bread
Department of Food Science and Technology IPB/DIN/2011

MATEM (E472f)
Synonyms : Diacetyltartaric-, acetic-, and fatty acids ester of glycerol, mixed Mono- and diglycerides of fatty acids esterified with acetic- and diacetylated tartaric acid

Solubility :
Dispersible in water Soluble in methanol, ethanol, acetone

ADI 0-50 mg/kg bw (JECFA)

Department of Food Science and Technology IPB/DIN/2011

Polysorbates
Polyoxyethylene esters of sorbitan monoesters

Department of Food Science and Technology IPB/DIN/2011

Chemical structure of Polysorbates

where w + x + y + z = approx. 20 and RCO- is the fatty acid moiety

Department of Food Science and Technology IPB/DIN/2011

Polysorbate 20
Polyoxyethylene (20) sorbitan monolaurate Solubility Soluble in water, ethanol, ethyl acetate, dioxane Insoluble in mineral oil and petroleum ether Safety : FDA CFR No. 172.515 Codex INS No. 432 ADI 0-25 mg/kg bw Lemon to amber colored oily liquid at 25oC, with a faint characteristic odor
Department of Food Science and Technology IPB/DIN/2011

Polysorbate 40
Polyoxyethylene (20) sorbitan monopalmitate Solubility Soluble in water, ethanol, methanol, ethyl acetate, and acetone Insoluble in mineral oil Lemon to orange colored, oily liquid or semi-gel at 25o, with a faint characteristic odor Safety : FDA CFR No. 172.515 Codex INS No. 434 ADI 0-25 mg/kg
Department of Food Science and Technology IPB/DIN/2011

Polysorbate 60
Polyoxyethylene (20) sorbitan monostearate (Tween 60) Soluble in water, ethyl acetate, anillin, and toluene Insoluble in mineral oil and vegetable oil Safety : FDA CFR No. 172.836 Codex INS No. 435 HLB = 14.9 Lemon to orange colored oily liquid or semi-gel at 25o, faint characteristic odor ADI 0-25 mg/kg Application Oil toppings, cake mixes, and cake icing
Department of Food Science and Technology IPB/DIN/2011

Polysorbate 65
Polyoxyethylene (20) sorbitan tristearate Dispersible in water Soluble in mineral oil, vegetable oil, petroleum ether, acetone, ether, dioxane, ethanol and methanol Safety FDA CFR No. 172.838 Codex INS No. 436 Tan coloured, waxy solid at 25oC,with a faint characteristic odour Permitted in ice cream, frozen food, custard
Department of Food Science and Technology IPB/DIN/2011

Polysorbate 80
Polyoxyethylene (20) sorbitan monooleate Solubility Soluble in water, ethanol, methanol, ethyl acetate and toluene Insoluble in mineral oil and petroleum ether Safety : FDA CFR No. 172.840 Codex INS No. 433 Lemon to amber coloured oily liquid at 25o, with a faint characteristic odour Application : Special dietetic foods Fat soluble vitamine
Department of Food Science and Technology IPB/DIN/2011

Sorbitan esters
Nomenclature and physical characteristic of sorbitan esters

Name Sorbitan monolaurate Sorbitan monostearate Sorbitan monooleat Sorbitan tristearate

E No. E 493 E 491 E 494 E 492

FDA Ref. CFR 172.842 Self-determined GRAS

Department of Food Science and Technology IPB/DIN/2011

Sorbitan monostearate
A mixture of the partial esters of sorbitol and its mono- and dianhydrides with edible stearic acid Solubility Soluble at temperatures above its melting point in toluene, dioxane, carbon tetrachloride, ether, methanol, ethanol and aniline Insoluble in petroleum ether and acetone Insoluble in cold water but dispersible in warm water Soluble with haze at temperatures above 50o in mineral oil and ethyl acetate
Department of Food Science and Technology IPB/DIN/2011

Sorbitan monostearate
ADI 0-25 mg/kg as the sum of sorbitan esters of lauric, oleic, palmitic and stearic acids HLB = 4.7 Safety : FDA CFR No. 172.842 Codex INS No. 491 Light cream to tan beads or flakes or hard, waxy solid with a slight characteristic odor

Department of Food Science and Technology IPB/DIN/2011

Stearoyl Lactylates
An ionic, hydrophylic emulsifier Lactic acid ester of monoglyceride with sodium or calcium Form strong complex with gluten in starch and especially valuable in baked products

Department of Food Science and Technology IPB/DIN/2011

Sodium stearoyl-2-lactylate
Chemical names :
Sodium di-2-stearoyl lactate, Sodium di-(2-stearoyloxy) propionate
major component

Synonyms :
Sodium stearoyl lactate Sodium stearoyl lactylate

Chemical formula C21H39O4Na; C19H35O4Na

(major components)
where R is C17H35 or C15H31 and the mean value of n is normally 2
Department of Food Science and Technology IPB/DIN/2011

Sodium stearoyl-2-lactylate
Solubility Insoluble in water, soluble in ethanol Safety FDA CFR No. 172.846 Codex INS No. 481 ADI 0-20 mg/kg

White or slightly yellowish powder or brittle solid with a characteristic odour Application : waffles, cake icing and filling, topping, non-dairy creamer, sauces and gravies
Department of Food Science and Technology IPB/DIN/2011

Calcium stearoyl-2-lactylate
Chemical names :
Calcium di-2-stearoyl lactate, Calcium di-(2-stearoyloxy) propionate
major component

Synonyms :
Calcium stearoyl lactate Calcium stearoyl lactylate

Chemical formula C42H78O8Ca; C38H70O8Ca

(major components)
where R is C17H35 or C15H31 and the mean value of n dependent on the proportion of lactic acid present
Department of Food Science and Technology IPB/DIN/2011

Calcium stearoyl-2-lactylate
Solubility : Slightly soluble in hot water Safety FDA CFR No. 172.844 Codex INS No. 482 ADI 0-20 mg/kg White or slightly yellowish powder or brittle solid with a characteristic odor Application : yeast-leavened bakery products, whipped topping, dehydrated potatoes
Department of Food Science and Technology IPB/DIN/2011

Polyglycerol Esters
HLB 6-11
a versatile emulsifier for food applications EU No number E475 FDA No number CFR 172.854

Polyglycerol Polyglycerol ester

Polyglycerol fatty acid esters, glycerin fatty acid ester Light yellow to amber, oily to very viscous liquids Light tan to medium brown, plastic or soft solids Light tan to brown, hard, waxy solids ADI 0-25 mg/kg bw
Department of Food Science and Technology IPB/DIN/2011

Affirmed GRAS Emulsifiers

184.1101 Diacetyl tartaric acid esters of monoand diglycerides 184.1323 Glyceryl monooleate 184.1324 Glyceryl monostearate 184.1328 Glyceryl behenate 184.1400 Lecithin 184.1505 Mono- and diglycerides 184.1521 Monosodium phosphate derivatives of mono- and diglycerides

Department of Food Science and Technology IPB/DIN/2011

Department of Food Science and Technology IPB/DIN/2011

Emulsifier usage in U.S.A (millions of pounds)

Emulsifier Mono&Di Lecithins MG Polysorb CSL/SSL PG ester SorbMS Bread 116 13.2 1.5 27 Cake mix M,SD,S* 23 1 0.5 1 0.75 10 0.1 30.5 10 2.5 0.75 0.25 1.8 2 Total 200 42.5 25 8 30 14.3 -

*Margarine, salad dressings, shortenings

Department of Food Science and Technology IPB/DIN/2011

Department of Food Science and Technology IPB/DIN/2011