Ethylene oxide

"Oxirane" redirects here. For oxiranes as a class of molecules, see epoxide.

Ethylene oxide
File:Ethylene-oxide-2D-skeletal.png	File:Ethylene-oxide-from-xtal-3D-balls.png
IUPAC name oxirane [1]
Other names epoxyethane, ethylene oxide, dimethylene oxide,oxacyclopropane
style="background: #F8EABA; text-align: center;" colspan="2" | Identifiers
Abbreviations	EO, EtO
CAS number	75-21-8 Y
PubChem	6354
EC number	200-849-9
KEGG	C06548
MeSH	Ethylene+Oxide
ChEBI	27561
RTECS number	KX2450000
SMILES
InChI
style="background: #F8EABA; text-align: center;" colspan="2" | Properties
Molecular formula	C2H4O
Molar mass	44.05 g mol−1
Appearance	colorless gas
Density	0.882 g/mL, 7.360 lbs/gallon
Melting point	−111.3 °C
Boiling point	10.7 °C
Solubility in water	miscible
style="background: #F8EABA; text-align: center;" colspan="2" | Thermochemistry
Std enthalpy of formation ΔfHo298	−52.6 kJ mol−1
Standard molar entropy So298	243 J mol−1 K−1
style="background: #F8EABA; text-align: center;" colspan="2" | Hazards
Main hazards	carcinogen
NFPA 704	75px 4 3 3
Flash point	−20 °C
Explosive limits	3 to 100%
style="background: #F8EABA; text-align: center;" colspan="2" | Related compounds
Related heterocycles	Aziridine, Ethylene sulfide, Borirane
Y (what is this?)  (verify) Except where noted otherwise, data are given for materials in their standard state (at 25 °C, 100 kPa)
Infobox references

Ethylene oxide, also called oxirane, is the organic compound with the formula C₂H₄O. This colorless flammable gas with a faintly sweet odor is the simplest epoxide, a three-membered ring consisting of two carbon and one oxygen atom. Because of its special molecular structure, ethylene oxide easily participates in the addition reaction, opening its cycle, and thus easily polymerizes. Ethylene oxide is isomeric with acetaldehyde. It is a strong poison to humans, showing carcinogenic, mutagenic, irritating and narcotic effects.

The major application of ethylene oxide is for producing many chemicals and intermediates, such as ethylene glycol, ethanolamines, simple and complex glycols, polyglycol ethers and other compounds. It is also a common gas-phase disinfectant which is widely used in hospitals to sterilize heat-sensitive tools and equipment. Ethylene oxide is industrially produced by direct oxidation of ethylene in the presence of silver catalyst. It is extremely flammable and explosive and is used as a main component of thermobaric weapons; therefore, it is commonly handled and shipped as a refrigerated liquid.

History

Ethylene oxide was first reported in 1859 by the French chemist Charles-Adolphe Wurtz, who prepared it by treating 2-chloroethanol with potassium hydroxide:

Cl–CH₂CH₂–OH + KOH → (CH₂CH₂)O + KCl + H₂O

Wurtz measured the boiling point of ethylene oxide as 13.5 °C, slightly higher than the present value, and discovered the ability of ethylene oxide to react with acids and salts of metals. Wurtz mistakenly assumed that ethylene oxide has the properties of an organic base. This delusion lasted until 1896 when Georg Bredig found that ethylene oxide is not an electrolyte. Its distinct difference with ethers, in particular, its propensity to join the addition reactions typical of unsaturated compounds, had long been a matter of debate. Only in 1893, the heterocyclic triangular structure of ethylene oxide had been proposed.

The first synthesis method had long remained the only, despite numerous attempts of scientists, including Wurtz himself, to produce ethylene oxide directly from ethyl. Only in 1931, French chemist Theodore Lefort developed a method of direct oxidation of ethylene in the presence of silver catalyst. Since 1940, almost all ethylene oxide produced industrially uses this method. Sterilization by ethylene oxide for the preservation of spices was patented in 1938 by the American chemist Lloyd Hall. Ethylene oxide achieved industrial importance during World War I as a precursor to both the coolant ethylene glycol and the chemical weapon mustard gas.

Molecular structure and properties

File:Ethylene-oxide.png

250px

The epoxy cycle of ethylene oxide is an almost regular triangle with bond angles of about 60° and a significant angular stress corresponding to the energy of 105 kJ/mol. For comparison, in alcohols the C–O–H angle is about 110°; in ethers, the C–O–C angle is 120°. The moment of inertia about the principal axes are I_A = 32.921×10⁻⁴⁰ g·cm², I_B = 37.926×10⁻⁴⁰ g·cm² and I_C = 59.510×10⁻⁴⁰ g·cm². The dipole moment at a temperature in the range 17–176 °C is 6.26×10⁻³⁰ C·m.

The relative instability of the carbon-oxygen bonds in the molecule is revealed by the comparison in the table of the energy required to break two C–O bonds in the ethylene oxide or one C–O bond in ethanol and dimethyl ether:

Reaction	ΔH°298, kJ/mol	Method
(C2H4)O → C2H4 + O (cleavage of two bonds)	354.38	Calculated, from atomic enthalpies
C2H5OH → C2H5 + OH (breaking one bond)	405.85	Electron impact
CH3OCH3 → CH3O + CH3 (breaking one bond)	334.72	Calculated using enthalpies of radicals formation

This instability determines the chemical activity of ethylene oxide and explains the ease of opening its cycle in addition reactions (see Chemical properties).

Physical properties

Ethylene oxide is a colorless gas at 25 °C and is a mobile liquid at 0 °C – viscosity of liquid ethylene oxide at 0 °C is about 5.5 times lower than that of water. The gas has a characteristic sweet odor of ether, noticeable when its concentration in air exceeds 500 ppm. Ethylene oxide is readily soluble in water, ethanol, diethyl ether and many organic solvents.

Main thermodynamical constants are:

• Standard molar heat capacity, C_p° = 48.19 J/(mol·K);
• Standard enthalpy of formation, ΔH°₂₉₈ = –51.037 kJ/mol;
• Standard entropy, S°₂₉₈ = 243.4 J/(mol·K);
• Gibbs free energy, ΔG°₂₉₈ = –11.68 kJ/mol;
• Heat of combustion, ΔH_c° = –1306 kJ/mol.

The surface tension of liquid ethylene oxide, at the interface with its own steam, is 35.8 mJ/m² at –50.1 °C and 27.6 mJ/m² at –0.1 °C.

The boiling point increases with the vapor pressure as follows: 57.7 (2 atm), 83.6 (5 atm) and 114.0 (10 atm).

Viscosity decreases with temperature with the values of 0.577 kPa·s at –49.8 °C, 0.488 kPa·s at –38.2 °C, 0.394 kPa·s at –21.0 °C and 0.320 kPa·s at 0 °C.

Between –91 °C and 10.5 °C, vapor pressure p (in mmHg) varies with temperature (T in °C) as lg p = 6.251 – 1115.1/(244.14 + T).

Properties of liquid ethylene oxide

Temperature, °C	Steam pressure, kPa	Enthalpy of the liquid, J/g	Enthalpy of vaporization, J/g	Density, kg/L	Heat capacity, J/(kg·K)	Thermal conductivity, W/(m·K)
–40 °C	8.35	0	628.6	0.9488	1878	0.20
–20 °C	25.73	38.8	605.4	0.9232	1912	0.18
0 °C	65.82	77.3	581.7	0.8969	1954	0.16
20 °C	145.8	115.3	557.3	0.8697	2008	0.15
40 °C	288.4	153.2	532.1	0.8413	2092	0.14
60 °C	521.2	191.8	505.7	0.8108	2247	0.14
80 °C	875.4	232.6	477.4	0.7794	2426	0.14
100 °C	1385.4	277.8	445.5	0.7443	2782	0.13
120 °C	2088	330.4	407.5	0.7052	3293	N/A*
140 °C	3020	393.5	359.4	0.6609	4225	N/A
160 °C	4224	469.2	297.1	0.608	N/A	N/A
180 °C	5741	551.2	222.5	0.533	N/A	N/A
195.8 °C	7191	N/A	N/A	N/A	N/A	N/A

*N/A – data not available.

Properties of ethylene oxide vapor

Temperature, K	Entropy, J/(mol·K)	Heat of formation, kJ/mol	Free energy of formation, kJ/mol	Viscosity Pa·s	Thermal conductivity, W/(m·K)	Heat capacity, J/(mol·K)
298	242.4	–52.63	–13.10	N/A	N/A	48.28
300	242.8	–52.72	–12.84	9.0	0.012	48.53
400	258.7	–56.53	1.05	13.5	0.025	61.71
500	274.0	–59.62	15.82	15.4	0.038	75.44
600	288.8	–62.13	31.13	18.2	0.056	86.27
700	302.8	–64.10	46.86	20.9	0.075	95.31
800	316.0	–65.61	62.80	N/A	0.090	102.9

*N/A – data not available.

Chemical properties

Ethylene oxide readily reacts with various compounds, breaking a C–O bond and opening the cycle. Its typical reactions are with nucleophiles which proceed via the S_N2 mechanism both in acidic (weak nucleophiles: water, alcohols) and alkaline media (strong nucleophiles: OH^–, RO^–, NH₃, RNH₂, RR'NH, etc.). The general reaction scheme is

Mechanism of reaction with ethylene oxide

and more specific reactions are described below.

Addition of water and alcohols

Aqueous solutions of ethylene oxide are rather stable and can exist for a long time without any noticeable chemical reaction, but adding a small amount of acid, such as strongly diluted sulfuric acid, immediately leads to the formation of ethylene glycol, even at room temperature:

(CH₂CH₂)O + H₂O → HO–CH₂CH₂–OH

The reaction also occurs in the gas phase, in the presence of a phosphoric acid salt as a catalyst.

The reaction is usually carried out at about 60 °C with a large excess of water, in order to prevent the reaction of the formed ethylene glycol with ethylene oxide that would form di- and triethylene glycol:

2 (CH₂CH₂)O + H₂O → HO–CH₂CH₂–O–CH₂CH₂–OH

3 (CH₂CH₂)O + H₂O → HO–CH₂CH₂–O–CH₂CH₂–O–CH₂CH₂–OH

The use of alkaline catalysts may lead to the formation of polyethylene glycol:

n (CH₂CH₂)O + H₂O → HO–(–CH₂CH₂–O–)_n–H

Reactions with alcohols proceed similarly yielding ethylene glycol ethers:

(CH₂CH₂)O + C₂H₅OH → HO–CH₂CH₂–OC₂H₅

2 (CH₂CH₂)O + C₂H₅OH → HO–CH₂CH₂–O–CH₂CH₂–OC₂H₅

Reactions with lower alcohols occur less actively than with water and require more severe conditions, such as heating to 160 °C and pressurizing to 3 MPa and adding an acid or alkali catalyst.

Reactions of ethylene oxide with fatty alcohols proceed in the presence of sodium metal, sodium hydroxide or boron trifluoride and are used for the synthesis of surfactants.

Addition of carboxylic acids and their derivatives

Reactions of ethylene oxide with carboxylic acids in the presence of a catalyst results in incomplete and with anhydrides in complete glycol esters:

(CH₂CH₂)O + CH₃COOH → HO–CH₂CH₂–OCOCH₃

(CH₂CH₂)O + (CH₃CO)₂O → CH₃COO–CH₂CH₂–OCOCH₃

The addition of acid amides proceeds similarly:

(CH₂CH₂)O + CH₃CONH₂ → HO–CH₂CH₂–NHCOCH₃

Addition of ethylene oxide to higher carboxylic acids is carried out at elevated temperatures (typically 140–180 °C) and pressure (0.3–0.5 MPa) in an inert atmosphere, in presence of an alkaline catalyst (concentration 0.01–2%), such as hydroxide or carbonate of sodium or potassium. The carboxylate ion acts as nucleophile in the reaction:

RCOOH + OH^– → RCOO^– + H₂O

(CH₂CH₂)O + RCOO^– → RCOOCH₂CH₂O^–

RCOOCH₂CH₂O^– + RCOOH → RCOOCH₂CH₂OH + RCOO^–

Adding ammonia and amines

Ethylene oxide reacts with ammonia forming a mixture of mono-, di- and triethanolamine. The reaction is stimulated by adding a small amount of water.

(CH₂CH₂)O + NH₃ → HO–CH₂CH₂–NH₂

2 (CH₂CH₂)O + NH₃ → HO–CH₂CH₂)₂NH₂

3 (CH₂CH₂)O + NH₃ → HO–CH₂CH₂)₃N

Similarly proceed the reactions with primary and secondary amines:

(CH₂CH₂)O + RNH₂ → HO–CH₂CH₂–NHR

Dialkylamino ethanols can further react with ethylene oxide, forming amino polyethylene glycols:

n (CH₂CH₂)O + R₂NCH₂CH₂OH → R₂NCH₂CH₂O–(–CH₂CH₂O–)_n–H

Trimethylamine reacts with ethylene oxide in the presence of water, forming choline:

(CH₂CH₂)O + (CH₃)₃N + H₂O → [HOCH₂CH₂N (CH₃)₃]⁺OH^–

Aromatic primary and secondary amines also react with ethylene oxide, forming the corresponding arylamino alcohols.

Halide addition

Ethylene oxide readily reacts with aqueous solutions of hydrochloric, hydrobromic and hydroiodic acids to form halohydrins. The reaction occurs easier with the last two acids:

(CH₂CH₂)O + HCl → HO–CH₂CH₂–Cl

The reaction with these acids competes with the acid-catalyzed hydration of ethylene oxide; therefore, there is always a by-product of ethylene glycol with an admixture of diethylene glycol. For a cleaner product, the reaction is conducted in the gas phase or in an organic solvent.

Ethylene fluorohydrin is obtained differently, by boiling hydrogen fluoride with a 5–6% solution of ethylene oxide in diethyl ether. The ether normally has a water content of 1.5–2%; in absence of water, ethylene oxide polymerizes.

Halohydrins can also be obtained by passing ethylene oxide through aqueous solutions of metal halides:

2 (CH₂CH₂)O + CuCl₂ + 2 H₂O → 2 HO–CH₂CH₂–Cl + Cu(OH)₂↓

Metalorganic addition

Interaction of ethylene oxide with organomagnesium compounds, which are Grignard reagents, can be regarded as nucleophilic substitution influenced by carbanion organometallic compounds. The final product of the reaction is a primary alcohol:

<math>\mathsf{(CH_2CH_2)O+RMgBr}\rightarrow\mathsf{R\!\!-\!\!CH_2CH_2\!\!-\!\!OMgBr\ \xrightarrow{H_2O}\ R\!\!-\!\!CH_2CH_2\!\!-\!\!OH}</math>

Similar mechanism is valid for other organometallic compounds, such as alkyl lithium:

<math>\mathsf{(CH_2CH_2)O+RLi}\rightarrow\mathsf{R\!\!-\!\!CH_2CH_2\!\!-\!\!OLi\ \xrightarrow{H_2O}\ R\!\!-\!\!CH_2CH_2\!\!-\!\!OH}</math>

Other addition reactions

Addition of hydrogen cyanide

Ethylene oxide easily reacts with the hydrogen cyanide forming ethylene cyanohydrin:

(CH₂CH₂)O + HCN → HO–CH₂CH₂–CN

A slightly chilled (10–20 °C) aqueous solution of calcium cyanide can be used instead of HCN:

2 (CH₂CH₂)O + Ca(CN)₂ + 2 H₂O → 2 HO–CH₂CH₂–CN + Ca(OH)₂

Ethylene cyanohydrin easily loses water, producing acrylonitrile:

HO–CH₂CH₂–CN → CH₂=CH–CN + H₂O

Addition of hydrogen sulfide and mercaptans

When reacting with the hydrogen sulfide, ethylene oxide forms 2-mercaptoethanol and thiodiglycol, and with alkylmercaptans it produces 2-alkyl mercaptoetanol:

(CH₂CH₂)O + H₂S → HO–CH₂CH₂–HS

2 (CH₂CH₂)O + H₂S → (HO–CH₂CH₂)₂S

(CH₂CH₂)O + RHS → HO–CH₂CH₂–SR

The excess of ethylene oxide with an aqueous solution of hydrogen sulfide leads to the tris-(hydroxyethyl) sulfonyl hydroxide:

3 (CH₂CH₂)O + H₂S → [(HO–CH₂CH₂)₃S⁺]OH^–

Addition of nitrous and nitric acids

Reaction of ethylene oxide with aqueous solutions of barium nitrite, calcium nitrite, magnesium nitrite, zinc nitrite or sodium nitrite leads to the formation of 2-nitroethanole:

2 (CH₂CH₂)O + Ca(NO₂)₂ + 2 H₂O → 2 HO–CH₂CH₂–NO₂ + Ca(OH)₂

With nitric acid, ethylene oxide forms mono- and dinitroglycols:

<math>\mathsf{(CH_2CH_2)O+HNO_3}\rightarrow\mathsf{HO\!\!-\!\!CH_2CH_2\!\!-\!\!ONO_2\ \xrightarrow[-H_2O]{+\ HNO_3}\ O_2NO\!\!-\!\!CH_2CH_2\!\!-\!\!ONO_2}</math>

Reaction with compounds containing active methylene groups

In the presence of alcoholates, reactions of ethylene oxide with compounds containing active methylene group leads to the formation of butyrolactones:

Synthesis of 2-acetylbutyrolactone

Additions with aromatic compounds

Ethylene oxide enters into the Friedel-Crafts reaction with benzene to form phenethyl alcohol:

Friedel-Crafts reaction with ethylene oxide

Styrene can be obtained in one stage if this reaction is conducted at elevated temperatures (315–440 °C) and pressures (0.35–0.7 MPa), in presence of an aluminosilicate catalyst.

Synthesis of crown ethers

A series of polynomial heterocyclic compounds, known as crown ethers, can be synthesized with ethylene oxide. One method is the cationic cyclopolymerization of ethylene oxide, limiting the size of the formed cycle:

n (CH₂CH₂)O → (–CH₂CH₂–O–)_n

To suppress the formation of other linear polymers the reaction is carried out in a highly dilute solution.

Reaction of ethylene oxide with sulfur dioxide in the presence of caesium salts leads to the formation of an 11-membered heterocyclic compound which has the complexing properties of crown ethers:

Synthesis of 1,3,6,9,2 λ 4-Tetraoksatia-2-tsikloundekanona

Isomerization

When ethylene oxide is heated to about 400 °C, or to 150–300 °C in the presence of a catalyst (Al₂O₃, H₃PO₄, etc.), it isomerizes into acetaldehyde:

<math>\mathsf{(CH_2CH_2)O\ \xrightarrow{200\ ^oC,\ Al_2O_3}\ CH_3CHO}</math>

The radical mechanism was proposed by Sidney W. Benson to explain this reaction in the gas phase; it comprises the following stages:

1) (CH₂CH₂)O ↔ •CH₂CH₂O• → CH₃CHO*

2) CH₃CHO* → CH₃• + CHO•

3) CH₃CHO* + M → CH₃CHO + M*

In reaction 3), M refers to the wall of the reaction vessel or to a heterogeneous catalyst. The moiety CH₃CHO* represents a short-lived (lifetime of 10^–8.5 seconds), activated molecule of acetaldehyde. Its excess energy is about 355.6 kJ/mol, which exceeds by 29.3 kJ/mol the binding energy of the C-C bond in acetaldehyde.

In absence of a catalyst, the thermal isomerization of ethylene oxide is never selective and apart from acetaldehyde yields significant amount of by-products (see section Thermal decomposition).

Reduction reaction

Ethylene oxide can be hydrogenated into ethanol in the presence of a catalyst, such as nickel, platinum, palladium, boranes, lithium aluminium hydride and some other hydrides.

<math>\mathsf{(CH_2CH_2)O+H_2\ \xrightarrow{80\ ^oC,\ Ni}\ C_2H_5OH}</math>

Conversely, with some other catalysts, ethylene oxide may be reduced by hydrogen to ethylene with the yield up to 70%. The reduction catalysts include mixtures of zinc dust and acetic acid, of lithium aluminium hydride with titanium trichloride (the reducing agent is actually titanium dichloride, formed by the reaction between LiAlH₄ and TiCl₂) and of iron(III) chloride with butyllithium in tetrahydrofuran.

<math>\mathsf{(CH_2CH_2)O+H_2\ \xrightarrow{Zn\ +\ CH_3COOH}\ CH_2\!\!=\!\!CH_2+H_2O}</math>

Oxidation

Ethylene oxide can further be oxidized, depending on the conditions, to glycolic acid or carbon dioxide:

<math>\mathsf{(CH_2CH_2)O+O_2\ \xrightarrow{AgNO_3}\ HOCH_2COOH}</math>

Deep gas-phase reactor oxidation of ethylene oxide at 800–1000 K and a pressure of 0.1–1 MPa yields a complex mixture of products containing O₂, H₂, CO, CO₂, CH₄, C₂H₂, C₂H₄, C₂H₆, C₃H₆, C₃H₈ and CH₃CHO.

Dimerization

In the presence of acid catalysts, ethylene oxide can be dimerized into dioxane:

Synthesis of dioxane

The reaction mechanism is as follows:

Mechanism of dimerization

The dimerization reaction is not selective, and there are always by-products, such as acetaldehyde (due to isomerization). The selectivity and speed of dimerization can be increased by adding a catalyst, such as platinum, platinum-palladium or iodine with sulfolan; however, 2-methyl-1,3-dioxolane is formed as a side product in the last case.

Polymerization

Liquid ethylene oxide can form a polyethyleneglycols. The polymerization can proceeds via radical and ionic mechanisms, but only the latter has a wide practical application. Cationic polymerization of ethylene oxide is assisted by protonic acids (HClO₄, HCl), Lewis acids (SnCl₄, BF₃, etc.), organometallic compounds or more complex reagents:

<math>\mathsf{n(CH_2CH_2)O\ \xrightarrow{SnCl_4}\ (-\!CH_2CH_2\!\!-\!\!O\!-)_n}</math>

The reaction mechanism is as follows. At the first stage, the catalyst (MX_m) is initiated by alkyl-or acylhalogen or by compounds with active hydrogen atoms, usually water, alcohol or glycol:

MX_m + ROH → MX_mRO^–H⁺

The resulting active complex reacts with ethylene oxide via the S_N2 mechanism:

(CH₂CH₂)O + MX_mRO^–H⁺ → (CH₂CH₂)O•••H⁺O^–RMX_m

(CH₂CH₂)O•••H⁺ O^–RMX_m → HO–CH₂CH₂⁺ + MX_mRO^–₂

HO–CH₂CH₂⁺ + n (CH₂CH₂)O → HO–CH₂CH₂–(O–CH₂CH₂)_n⁺

The chain breaks as

HO–CH₂CH₂–(O–CH₂CH₂)_n⁺ + MX_mRO^– → HO–CH₂CH₂–(O–CH₂CH₂)_n–OR + MX_m

H(O–CH₂CH₂)_n–O–CH₂–CH₂⁺ + MX_mRO^– → H(O–CH₂CH₂)_n–O–CH=CH₂ + MX_m + ROH

Anionic polymerization of ethylene oxide is assisted by bases, such as alcoholates hydroxides, carbonates or other compounds of alkali or alkaline earth metals. The reaction mechanism is as follows:

(CH₂CH₂)O + RONa → RO–CH₂CH₂–O^–Na⁺

RO–CH₂CH₂–O^–Na⁺ + n (CH₂CH₂)O → RO–(CH₂CH₂–O)_n–CH₂CH₂–O^–Na⁺

RO–(CH₂CH₂–O)_n–CH₂CH₂–O^–Na⁺ → RO–(CH₂CH₂–O)_n–CH=CH₂ + NaOH

RO–(CH₂CH₂–O)_n–CH₂CH₂–O^–Na⁺ + H₂O → RO–(CH₂CH₂–O)_(n+1)OH + NaOH

Thermal decomposition

Ethylene oxide is relatively stable to heating – in the absence of a catalyst, it does not dissociate up to 300 °C, and only above 570 °C there is a major exothermic decomposition, which proceeds through the radical mechanism. The first stage involves isomerization, however high temperature accelerated the radical processes. They result in a gas mixture containing acetaldehyde, ethane, ethyl, methane, hydrogen, carbon dioxide, ketene and formaldehyde. High-temperature pyrolysis (830–1200 K) at elevated pressure in an inert atmosphere leads to a more complex composition of the gas mixture, which also contains acetylene and propane. Contrary to the isomerization, initiation of the chain occurs mainly as follows:

(CH₂CH₂)O → •CH₂CH₂O• → CH₂O + CH₂:

When carrying the thermal decomposition of ethylene oxide in the presence of transition metal compounds as catalysts, it is possible not only to reduce its temperature, but also to have ethyl as the main product, that is to reverse the ethylene oxide synthesis reaction.

Other reactions

Thiocyanate ions or thiourea transform ethylene oxide into thiiranes (ethylene sulfides):

(CH₂CH₂)O + (NH₂)₂C=S → (CH₂CH₂)S + (NH₂)₂C=O

mechanism synthesis thiiranes of ethylene oxide under the influence of thiocyanate ion

Reaction of phosphorus pentachloride with ethylene oxide produces ethylene dichloride:

(CH₂CH₂)O + PCl₅ → Cl–CH₂CH₂–Cl + POCl₃

Other dichloro derivatives of ethylene oxide can be obtained by combined action of sulfuryl chloride (SOCl₂) and pyridine and of triphenylphosphine and carbon tetrachloride.

Phosphorus trichloride reacts with ethylene oxide forming chloroethyl esters of phosphorous acid:

(CH₂CH₂)O + PCl₃ → Cl–CH₂CH₂–OPCl₂

2 (CH₂CH₂)O + PCl₃ → (Cl–CH₂CH₂–O)₂PCl

3 (CH₂CH₂)O + PCl₃ → Cl–CH₂CH₂–O)₃P

The reaction product of ethylene oxide with acyl chlorides in the presence of sodium iodide is a complex iodoethyl ether:

(CH₂CH₂)O + RCOCl + NaI → RC(O)–OCH₂CH₂–I + NaCl

Heating ethylene oxide to 100 °C with carbon dioxide, in a non-polar solvent in the presence of bis-(triphenylphosphine)-nickel(0) results in ethylene carbonate:

Synthesis of ethylene carbonate

In industry, a similar reaction is carried out at high pressure and temperature in the presence of quaternary ammonium or phosphonium salts as a catalyst.

Reaction of ethylene oxide with formaldehyde at 80–150 °C in the presence of a catalyst leads to the formation of 1,3-dioxolane:

Synthesis of 1,3-dioxolane

Substituting formaldehyde by other aldehydes or ketones results in a 2-substituted 1,3-dioxolane (yield: 70–85%, catalyst: tetraetilammoniybromid).

Catalytic hydroformylation of ethylene oxide results in hydroxypropanal and further in propane-1,3-diol:

<math>\mathsf{(CH_2CH_2)O+CO+H_2}\rightarrow\mathsf{CHO\!\!-\!\!CH_2CH_2\!\!-\!\!OH\ \xrightarrow{+H_2}\ HO\!\!-\!\!CH_2CH_2CH_2\!\!-\!\!OH}</math>

Laboratory synthesis

Dehydrochlorination of ethylene and its derivatives

Dehydrochlorination of 2-chloroethanol, developed by Wurtz back in 1859, still remains one of the most common laboratory methods of producing ethylene oxide:

Cl–CH₂CH₂–OH + NaOH → (CH₂CH₂)O + NaCl + H₂O

The reaction is carried out at elevated temperature, and beside sodium hydroxide or potassium hydroxide, calcium hydroxide, barium hydroxide, magnesium hydroxide or carbonates of alkali or alkaline earth metals can be used.

Chloroethanol, in turn, is synthesized using one of the following methods:

By reacting ethylene glycol hydrochloric acid:

OH–CH₂CH₂–OH + HCl → OH–CH₂CH₂–Cl + H₂O

By reacting ethylene with hypochlorous acid:

CH₂=CH₂ + HOCl → OH–CH₂CH₂–Cl

or by chlorination of ethylene

CH₂=CH₂ + Cl₂ + H₂O → OH–CH₂CH₂–Cl + HCl

Another convenient and old method of ethylene oxide synthesis is reaction of an alkali with chloroethyl acetate:

Cl–CH₂CH₂–OCOCH₃ + 2 KOH → (CH₂CH₂)O + KCl + CH₃COOK + H₂O

With a high yield (90%) ethylene oxide can be produced by reacting calcium oxide with ethyl hypochlorite; substituting calcium by other alkaline earth metals reduces the reaction yield:

2 CH₃CH₂–OCl + CaO → 2 (CH₂CH₂)O + CaCl₂ + H₂O

In turn, ethylhypochlorite is synthesized as follows:

Cl₂ + NaOH + CH₃CH₂OH → CH₃CH₂OCl + NaCl + H₂O

Direct oxidation of ethylene by peroxy acids

Ethylene can be directly oxidized into ethylene oxide using peroxy acids, for example, peroxybenzoic or meta-chloro-peroxybenzoic acid:

Oxidation of ethylene by peroxy acids

Oxidation by peroxy acids is efficient for higher alkenes, but not for ethylene. The above reaction is slow and has low yield, therefore it is not used in the industry.

Other preparative methods

Other synthesis methods include reaction of diiodo ethane with silver oxide:

I–CH₂CH₂–I + Ag₂O → (CH₂CH₂)O + 2 AgI

and decomposition of ethylene carbonate at 200–210 °C in the presence of hexachloroethane:

Decomposition of ethylene carbonate

Industrial synthesis

History

Commercial production of ethylene oxide dates back to 1914 when BASF built the first factory which used the chlorohydrin process (reaction of ethylene chlorohydrin with calcium hydroxide). The chlorohydrin process was unattractive for several reasons, including low efficiency and loss of valuable chlorine into calcium chloride. More efficient direct oxidation of ethylene by air was invented by Lefort in 1931 and in 1937 Union Carbide opened the first plant using this process. It was further improved in 1958 by Shell Oil Co. by replacing air with oxygen and using elevated temperature of 200–300 °C and pressure (1–3 MPa). This more efficient routine accounted for about half of ethylene oxide production in the 1950s in the U.S., and after 1975 it completely replaced the previous methods.

Chlorohydrin process of production of ethylene oxide

Although the chlorohydrin process is almost entirely superseded in the industry by the direct oxidation of ethylene, the knowledge of this method is still important for educational reasons and because it is still used in the production of propylene oxide. The process consists of three major steps: synthesis of ethylene chlorohydrin, dehydrochlorination of ethylene chlorohydrin to ethylene oxide and purification of ethylene oxide. Those steps are carried continuously. In the first column, hypochlorination of ethylene is carried out as follows:

Cl₂ + H₂O → HOCl + HCl

CH₂=CH₂ + HOCl → OH–CH₂CH₂–Cl

CH₂=CH₂ + Cl₂ → Cl–CH₂CH₂–Cl

To suppress the conversion of ethylene into the ethylene dichloride (the last reaction), the concentration of ethylene is maintained at about 4–6%, and the solution is heated by steam to the boiling point.

Next, aqueous solution of ethylene chlorohydrin enters the second column, where it reacts with a 30% solution of calcium hydroxide at 100 °C:

2 OH–CH₂CH₂–Cl + Ca(OH)₂ → 2 (CH₂CH₂)O + CaCl₂ + H₂O

The produced ethylene oxide is purified by rectification. The chlorohydrin process allows to reach 95% conversion of ethylene chlorohydrin. The yield of ethylene oxide is about 80% of the theoretical value; for 1 ton of ethylene oxide, about 200 kg of ethylene dichloride is produced.

Direct oxidation of ethylene

Usage in the global industry

Direct oxidation of ethylene was patented by Lefort in 1931. This method was repeatedly modified for industrial use, and at least four major variations are known. They all use oxidation by oxygen or air and a silver-based catalyst, but differ in the technological details and hardware implementations.

Union Carbide (currently a division of Dow Chemical Company) was the first company to develop the direct oxidation process. Since 1994, it uses the so-called METEOR process (Most Effective Technology for Ethylene Oxide Reactions) which is characterized by high productivity, low initial capital investment and low operating costs. The method is the exclusive property of the company; it is used only at its own plants and accounts for about 20% of the global ethylene oxide production.

A similar production method was developed by Scientific Design Co., but it received wider use because of the licensing system – it accounts for 25% of the world's production and for 75% of world's licensed production of ethylene oxide. A proprietary variation of this method is used by Japan Catalytic Chemical Co., which adapted synthesis of both ethylene oxide and ethylene glycol in a single industrial complex.

A different modification was developed Shell International Chemicals BV. Their method is rather flexible with regard to the specific requirements of specific industries; it is characterized by high selectivity with respect to the ethylene oxide product and long lifetime of the catalyst (3 years). It accounts for about 40% of global production.

Older factories typically use air for oxidation whereas newer plants and processes, such as METEOR and Japan Catalytic, favor oxygen.

Chemistry and kinetics of the direct oxidation process

Formally, the direct oxidation process is expressed by the following equation:

<math>\mathsf{2CH_2\!\!=\!\!CH_2+O_2\ \xrightarrow{Ag}\ 2(CH_2CH_2)O}</math>

However, significant yield of carbon dioxide and water is observed in practice, which can be explained by the complete oxidation of ethylene or ethylene oxide:

CH₂=CH₂ + 3 O₂ → 2 CO₂ + 2 H₂O

2 (CH₂CH₂)O + 5 O₂ → 4 CO₂ + 4 H₂O

The process of heterogeneous catalytic oxidation of ethylene was studied by P. A. Kilty and W. M. H. Sachtler, who suggested the following mechanism:

O₂ + 4 Ag(adj) → 4 Ag + 2 O^2–(ads)

O₂ + Ag → Ag⁺ + O₂^–

O₂^–(ads) + CH₂=CH₂ → (CH₂CH₂)O + O(ads)

6 O (ads) + CH₂=CH₂ → 2 CO₂ + 2 H₂O

Here (ads) refers to particles adsorbed on the catalyst surface and (adj) to particles of silver, directly adjacent to the oxygen atoms.

Thus the overall reaction is expressed as

7 CH₂=CH₂ + 6 O₂ → 6 (CH₂CH₂)O + 2 CO₂ + 2 H₂O

and the maximum degree of conversion of ethylene to ethylene oxide is 6/7 or 85.7%.

The catalyst for the reaction is metallic silver deposited on various matrixes, including pumice, silica gel, various silicates and aluminosilicates, alumina and silicon carbide, and activated by certain additives (antimony, bismuth, barium peroxide, etc.). The process temperature was optimized as 220–280 °C. Lower temperatures reduce the activity of the catalyst, and higher temperatures promote the complete oxidation of ethylene thereby reducing the yield of ethylene oxide. Elevated pressure of 1–3 MPa increases the productivity of the catalyst and facilitates absorption of ethylene oxide from the reacting gases.

Whereas oxidation by air is still being used, oxygen (> 95% purity) is preferred for several reasons, such as higher molar yield of ethylene oxide (75–82% for oxygen vs. 63–75% for air), higher reaction rate (no gas dilution) and no need of separating nitrogen in the reaction products.

World production of ethylene oxide

The world production of ethylene oxide was 19 million tonnes in 2008 and 18 million tonnes in 2007. This places ethylene oxide 14th most produced organic chemical, whereas the most produced one was ethylene with 113 million tonnes. SRI Consulting forecasted the growth of consumption of ethylene oxide of 4.4% per year during 2008–2013 and 3% from 2013 to 2018.

In 2004, the global production of ethylene oxide by region was as follows:

Region	Number of major producers	Production, thousand tonnes
North America United States Canada Mexico	10 3 3	4009 1084 350
South America Brazil Venezuela	2 1	312 1982
Europe Belgium France Germany Netherlands Spain Turkey United Kingdom Eastern Europe	2 1 4 2 1 1 1 no data	770 215 995 460 100 115 300 950
Middle East Iran Kuwait Saudi Arabia	2 1 2	201 350 1781
Asia China Taiwan India Indonesia Japan Malaysia South Korea Singapore	No data 4 > 2 1 4 1 3 1	1354 820 488 175 949 385 740 80

The world's largest producers of ethylene oxide are Dow Chemical Company (3–3.5 million tonnes in 2006), Saudi Basic Industries (2000–2500 tonnes in 2006), Royal Dutch Shell (1.328 million tonnes in 2008–2009), BASF (1.175 million tonnes in 2008–2009), China Petrochemical Corporation (~1000 tonnes in 2006), Formosa Plastics (~1 million tonnes in 2006) and Ineos (0.92 million tonnes in 2008–2009).

Applications

File:Eo-usesEN.png

Global industrial use of ethylene oxide in 2007.

Ethylene oxide is one of the most important raw materials used in the large-scale chemical production. Most ethylene oxide is used for synthesis of ethylene glycols, including diethylene glycol and triethylene glycol, that accounts for up to 75% of global consumption. Other important products include ethylene glycol ethers, ethanolamines and ethoxylates. Among glycols, ethylene glycol is used as antifreeze, in the production of polyester and polyethylene terephthalate (PET – raw material for plastic bottles), liquid coolants and solvents. Polyethyleneglycols are used in perfumes, cosmetics, pharmaceuticals, lubricants, paint thinners and plasticizers. Ethylene glycol ethers are part of brake fluids, detergents, solvents, lacquers and paints. Other products of ethylene oxide. Ethanolamines are used in the manufacture of soap and detergents and for purification of natural gas. Ethoxylates are reaction products of ethylene oxide with higher alcohols, acids or amines. They are used in the manufacture of detergents, surfactants, emulsifiers and dispersants.

Whereas synthesis of ethylene glycols is the major application of ethylene oxide, its percentage varies greatly depending on the region: from 44% in the Western Europe, 63% in Japan and 73% in North America to 90% in the rest of Asia and 99% in Africa.

Production of ethylene glycol

Ethylene glycol is industrially produced by non-catalytic hydration of ethylene oxide at a temperature of 200 °C and a pressure of 1.5–2 MPa:

(CH₂CH₂)O + H₂O → HOCH₂CH₂OH

By-products of the reaction are diethylene glycol, triethylene glycol and polyglycols with the total of about 10%, which are separated from the ethylene glycol by distillation at reduced pressure.

Another synthesis method is the reaction of ethylene oxide and CO₂ (temperature 80–120 °C and pressure of 5.2 MPa) yielding ethylene carbonate and its subsequent hydrolysis with decarboxylation:

<math>\mathsf{(CH_2CH_2)O+CO_2}\rightarrow\mathsf{(O\!\!-\!\!CH_2CH_2\!\!-\!\!O)C\!\!=\!\!O\ \xrightarrow[-CO_2]{+H_2O}\ HOCH_2CH_2OH}</math>

Modern technologies of production of ethylene glycol include the following. Shell OMEGA technology (Only Mono-Ethylene Glycol Advantage) is a two-step synthesis of ethylene carbonate using a phosphonium halide as a catalyst. The glycol yield is 99–99.5%, with other glycols practically absent. The main advantage of the process is production of pure ethylene glycol without the need for further purification. The first commercial plant which uses this method was opened in 2008 in South Korea. Dow METEOR (Most Effective Technology for Ethylene Oxide Reactions) is an integrated technology for producing ethylene oxide and its subsequent hydrolysis into ethylene glycol. The glycol yield is 90–93%. The main advantage of the process is relative simplicity, using fewer stages and less equipment.

Production of glycol ethers

The major industrial esters of mono-, di- and triethylene glycols are methyl, ethyl and normal butyl ethers, as well as their acetates and phthalates. The synthesis involves reaction of the appropriate alcohol with ethylene oxide:

(CH₂CH₂)O + ROH → HOCH₂CH₂OR

(CH₂CH₂)O + HOCH₂CH₂OR → HOCH₂CH₂OCH₂CH₂OR

(CH₂CH₂)O + HOCH₂CH₂OCH₂CH₂OR → HOCH₂CH₂OCH₂CH₂OCH₂CH₂OR

The reaction of monoesters with an acid or its anhydride leads to the formation of the esters:

CH₃COOH + HOCH₂CH₂OR → ROCH₂CH₂OCOCH₃ + H₂O

Production of ethanolamines

In the industry, ethanolamines (mono-, di- and triethanolamines) are produced by reacting ammonia and ethylene oxide in anhydrous medium at a temperature of 40–70 °C and pressure of 1.5–3.5 MPa:

CH₂CH₂)O + NH₃ → HOCH₂CH₂NH₂

2 (CH₂CH₂)O + NH₃ → (HOCH₂CH₂)₂NH

3 (CH₂CH₂)O + NH₃ → (HOCH₂CH₂)₃N

All three ethanolamines are produced in the process, while ammonia and part of methylamine are recycled. The final products are separated by vacuum distillation. Hydroxyalkylamines are produced in a similar process:

CH₂CH₂)O + RNH₂ → HOCH₂CH₂NHR

2 (CH₂CH₂)O + RNH₂ → (HOCH₂CH₂)₂NR

Monosubstituted products are formed by reacting a large excess of amine with ethylene oxide in presence of water and at a temperature below 100 °C. Disubstituted products are obtained with a small excess of ethylene oxide, at a temperature of 120–140 °C and a pressure of 0.3–0.5 MPa.

Production of ethoxylates

Industrial production of ethoxylates is realized by a direct reaction of higher alcohols, acids or amines with ethylene oxide in the presence of an alkaline catalyst at a temperature of 120–180 °C. Modern plants producing ethoxylates are usually based on the BUSS LOOP reactors technology, which is based on a three-stage continuous process. In the first stage, the initiator or catalyst of the reaction and the feedstock are fed into the container, where they are mixed, heated and vacuum dried. Then reaction is carried out in a special insulated reactor in an inert atmosphere (nitrogen) to prevent a possible explosion of ethylene oxide. Finally, the reaction mixture is neutralized, degassed and purified.

Production of acrylonitrile

Currently, most acrylonitrile (90% in 2008) is produced by the SOHIO method, which is based on the catalytic oxidation of propylene in the presence of ammonia and bismuth phosphomolybdate. However, until 1960 a key production process was addition of hydrogen cyanide to ethylene oxide, followed by dehydration of the resulting cyanohydrin::

<math>\mathsf{(CH_2CH_2)O+HCN}\rightarrow\mathsf{HOCH_2CH_2CN\ \xrightarrow[-H_2O]\ CH_2\!\!=\!\!CH\!\!-\!\!CN }</math>

Addition of hydrocyanic acid to ethylene oxide is carried out in the presence of a catalyst (sodium hydroxide and diethylamine), and dehydration of cyanohydrin occurs in the gas phase upon the catalytic action of aluminium oxide.

Other uses

The direct use of ethylene oxide accounts for only 0.05% (2004 data) of its global production. Ethylene oxide is used as a fumigant and disinfecting agent, as a mixture with carbon dioxide (8.5–80% of ethylene oxide), nitrogen or dichlorodifluoromethane (12% ethylene oxide). It is applied for gas-phase sterilization of medical equipment and instruments, packaging materials and clothing, surgical and scientific equipment; for processing of storage facilities (tobacco, packages of grain, sacks of rice, etc.), clothing, furs and valuable documents.

Ethylene oxide is also used as a flame retardant, accelerator of maturation of tobacco leaves and fungicide. Ethylene oxide is also used as a main component of thermobaric weapons (fuel-air explosives).

Identification of ethylene oxide

The simplest qualitative reaction for ethylene oxide uses its property to precipitate insoluble hydroxides of metals when it is passed through aqueous solutions of their salts, for example

2 (CH₂CH₂)O + MnCl₂ + 2 H₂O → 2 HO–CH₂CH₂–Cl + Mn(OH)₂↓

Similarly, ethylene oxide is detected by the bright pink color of the indicator when passing air through aqueous solutions of some salts of sodium or potassium (chlorides, iodides, thiosulfates, etc.) with the addition of phenolphthalein:

(CH₂CH₂)O + NaCl + H₂O → HO–CH₂CH₂–Cl + NaOH

Other methods of ethylene oxide detection are color reactions with pyridine derivatives and hydrolysis of ethylene glycol with periodic acid. The produced iodic acid is detected with silver nitrate.

The main physical method of ethylene oxide detection is gas chromatography.

Fire and explosion hazards

Ethylene oxide is extremely flammable and its mixtures with air are explosive. When heated, it may rapidly expand causing fire and explosion. The autoignition temperature is 429 °C, minimum inflammable content in the air is 2.7%, and the NPFA rating is NFPA 704.

Fires caused by ethylene oxide are extinguished by traditional media, including foam, carbon dioxide or water. Extinguishing of burning ethylene oxide is complicated by that it can continue burning in an inert atmosphere and in water solutions. Fire suppression is reached only upon dilution with water above 22:1.

Physiological effects

Effect on microorganisms

Ethylene oxide inhibits growth of microorganisms (disinfectant properties) and when present in high concentrations, can completely destroy them. Strong alkylating properties make ethylene oxide a universal poison for protoplasm: it causes clotting of proteins, deactivation of enzymes and other biologically important components of a living organism.

Ethylene oxide acts more strongly against bacteria, especially gram-positive bacteria, than against yeast and fungi. The disinfectant effect of ethylene oxide is similar to that of sterilization by heat, but because of limited penetration, it affects only the surface. The Sterility Assurance Level, after a certain specified exposure to ethylene oxide is 10⁻⁶, meaning that the chance of finding a single bacterium is below 1 per million.

Effects on humans and animals

Ethylene oxide is an alkylating agent; it has irritating, sensitizing and narcotic effects. Chronic exposure to ethylene oxide also induces mutagenic effects. The International Agency for Research on Cancer classifies ethylene oxide into group 1, meaning it is a proven carcinogen. A 2003 study of 7,576 women exposed while at work in commercial sterilization facilities in the U.S. suggests ethylene oxide is associated with breast cancer incidence. A 2004 follow up study analyzing 18,235 men and women workers exposed to ethylene oxide from 1987 to 1998 concluded "There was little evidence of any excess cancer mortality for the cohort as a whole, with the exception of bone cancer based on small numbers. Positive exposure-response trends for lymphoid tumors were found for males only. Reasons for the sex specificity of this effect are not known. There was also some evidence of a positive exposure-response for breast cancer mortality."

Ethylene oxide is toxic by inhalation with an U.S. OSHA permissible exposure limit of 1 ppm calculated as a time weighted average (TWA) over 8 hours of 1 ppm, and a short term exposure limit (excursion limit) calculated as a TWA over 15 minutes of 5 ppm. [29 CFR 19101.1048]. At concentrations in the air about 200 parts per million, ethylene oxide irritates mucous membranes of the nose and throat; higher contents cause damage to the trachea and bronchi, progressing into the partial collapse of the lungs. High concentrations can cause pulmonary edema and damage the cardiovascular system; the damaging effect of ethylene oxide may occur only after 72 hours after exposure. The maximum content of ethylene oxide in the air according to the U.S. standards (ACGIH) is 1.8 mg/m³. NIOSH has determined that the Immediately Dangerous to Life and Health level (IDLH) is 800 ppm. Because the odor threshold for ethylene oxide varies between 250 and 700 ppm, it is imperceptible to human until well above dangerous levels. Therefore continuous monitors are standard practice. Currently, the substance is banned from the use for plant protection by the EU government.

Ethylene oxide causes acute poisoning, accompanied by the following symptoms: slight heartbeat, muscle twitching, flushing, headache, diminished hearing, acidosis, vomiting, dizziness, transient loss of consciousness and a sweet taste in the mouth. Acute intoxication is accompanied by a strong throbbing headache, dizziness, difficulty in speech and walking, sleep disturbance, pain in the legs, weakness, stiffness, sweating, increased muscular irritability, transient spasm of retinal vessels, enlargement of the liver and suppression of its antitoxic functions.

Ethylene easily penetrates through the clothing and footwear, causing skin irritation and dermatitis with the formation of blisters, fever and leukocytosis.

The median lethal doses (LD₅₀, or a dose required to kill half the members of a tested population after a certain time) for ethylene oxide are 72 mg/kg (rat, oral) and 187 mg/kg (rat, subcutaneous injection).

External links

• EOSA Promoting the safe use of Ethylene Oxide for Sterilization
• WebBook page for C2H4O
• National Pollutant Inventory – Ethylene oxide fact sheet
• Ethylene Oxide User's Guide
• Ethylene Oxide MSDS (Material Safety Data Sheet).
• National Institute for Occupational Safety and Health – Ethylene Oxide Topic Page
• EOSA memo about Ethylene Oxide (EtO) facts

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